JP2005200044A - Plastic container and manufacturing method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic container, which improves fitness for packaging and preserving a content, and a manufacturing method for the container. <P>SOLUTION: The plastic container B is manufactured by forming a level surface 2 containing irregularities on the entire inner surface of a plastic molded container body 1, using a plasma process, and then forming a gas barrier thin film 3, which is composed mainly of an inorganic oxide, on the whole of the level surface 2. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a plastic container and a method for producing the same.

Conventionally, as one of packaging containers for filling and packaging various articles, there are plastic containers having various forms manufactured by various molding methods such as injection molding, extrusion molding, and blow molding.
These plastic containers are lighter, harder to break, cheaper, easier to manufacture, easier to mass-produce, easier to handle, and more than glass containers. Today, it is indispensable as a packaging container for filling and packaging various articles and is used in various fields.
However, the plastic container described above has various advantages, but has several disadvantages.
One of the disadvantages is that the gas permeability of oxygen gas, water vapor, carbon dioxide gas, etc. is high.
For example, stretch-blow molded containers made of polyester resin or polyolefin resin can cause the gas in the atmosphere to enter the molded container, or the components in the package contents can be released to the outside of the container. There is a problem in that it has a great influence, alters, modifies, or deteriorates the quality of the product and causes a reduction in shelf life.
In the plastic container, plasticizers, stabilizers, other additives, residual monomers, etc. contained in the plastic composition are eluted, and these affect the quality of the package contents. In some cases, the quality may be altered or modified so that it is no longer used.

By the way, in order to improve the above-mentioned problems in the plastic container, the present applicant firstly provides a gas barrier thin film mainly composed of an inorganic oxide on the entire inner surface of the plastic container body. Proposing a plastic container characterized by further providing a sterilization surface by plasma treatment on the entire inner surface of the plastic container body, and further providing a gas barrier thin film on the entire surface including the sterilization surface. A plastic container has been proposed (see, for example, Patent Document 1 and Patent Document 2).
JP2003-95272A. JP2003-95273A.

However, in the above Patent Documents 1 and 2, when a plastic container is manufactured, in order to form a gas barrier thin film excellent in gas barrier performance that prevents permeation of oxygen gas, water vapor, etc., the inner surface of the container main body and the gas barrier are formed. Conditions such as adhesion to the conductive thin film, film thickness of the gas barrier thin film, film quality accompanying the film thickness, film performance, etc. must be prepared, resulting in a longer deposition process time, for example, obtained There is a problem that a plastic container is expensive.
Furthermore, in the above Patent Documents 1 and 2, it is necessary to keep the plastic container main body at high temperature and high vacuum at the time of vapor deposition. In this case, if the vapor deposition process time becomes long, for example, the plastic container main body If it contains a lot of water, the moisture acts as an outgas during vapor deposition, which not only lengthens the vacuuming time, but also affects the adhesion between the inner surface of the plastic container body and the gas barrier thin film. There is a problem that it is extremely difficult to manufacture a preferable plastic container.
In addition, if the vapor deposition process time becomes longer as described above, the plastic container body is affected by heat during the vapor deposition, and the plastic container body itself is deformed, and there is a problem that a defective appearance product is produced. It is.
Furthermore, in the above Patent Documents 1 and 2, it is difficult to cause plasma to collide with the inner surface of the plastic container body at an acceleration during vapor deposition, so that the gas barrier performance that prevents the transmission of oxygen gas, water vapor, and the like. In addition, there is a problem that it is extremely difficult to form a gas barrier thin film having excellent characteristics.
Therefore, the present invention forms a gas barrier thin film excellent in gas barrier performance that prevents permeation of oxygen gas, water vapor, and the like on the entire inner surface of the plastic molded container body, thereby forming a filling of the contents. It is to provide a plastic container excellent in packaging suitability, storage suitability and the like.

  As a result of various studies to improve the problems as described above, the present inventor has paid attention to the fact that when the surface of a plastic substrate is subjected to plasma treatment, an uneven smooth surface is formed by the plasma treatment. The entire inner surface of the molding container main body is subjected to plasma treatment using, for example, a low temperature plasma chemical vapor deposition apparatus to form an uneven smooth surface by the plasma treatment, and then the entire surface including the uneven smooth surface. A plastic container is manufactured by forming a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide, and then the packaged product is filled and packaged with contents such as food and drink in the plastic container. As a result, the main surface of the inner surface of the plastic molded container body is mainly made of an inorganic oxide such as silicon oxide without causing deformation of the plastic molded container body itself. The gas barrier film that shortens the deposition process time and adheres extremely firmly, and the adhesion between the two is extremely high. Further, this prevents the gas barrier from permeating oxygen gas, water vapor, carbon dioxide gas, etc. The present invention has been completed by finding that it is possible to produce a plastic container excellent in filling and packaging properties, storage suitability, etc. for various contents such as foods and drinks.

  That is, the present invention provides an uneven smooth surface by plasma treatment on the entire inner surface of a plastic molded container body, and further laminates a gas barrier thin film mainly composed of an inorganic oxide on the entire surface including the uneven smooth surface. The present invention relates to a plastic container and a manufacturing method thereof.

According to the present invention, a gas barrier thin film mainly composed of an inorganic oxide can be very strongly and closely bonded to the inner surface of a plastic molded container body through an uneven smooth surface formed by plasma treatment. It is possible to manufacture a plastic container excellent in gas barrier property that prevents permeation of carbon dioxide gas and the like.
Furthermore, the present invention does not show deformation due to heat during the vapor deposition of the plastic molded container body, and a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is deposited on the inner surface of the plastic molded container body for the vapor deposition process time. It can be shortened and can be extremely firmly attached.
In addition, the present invention reduces the moisture content of the plastic molded container body as much as possible, so that the influence of outgassing due to moisture and the like during vapor deposition is not recognized, and as a result, it is easy to maintain the degree of vacuum. A gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide can be deposited on the inner surface of the plastic molded container body with a reduced deposition process time and extremely firmly.

Hereinafter, the plastic container according to the present invention will be described in more detail with reference to the drawings.
[Embodiment 1]
First, a first embodiment of a plastic container according to the present invention will be described.
FIG. 1 is a schematic configuration diagram showing a schematic configuration of a low-temperature plasma chemical vapor deposition apparatus according to Embodiment 1 used for manufacturing a plastic container according to the present invention.
As shown in FIG. 1, the low-temperature plasma chemical vapor deposition apparatus A includes an external electrode 12 and an internal electrode 16.
The external electrode 12 includes a first external partial electrode 12a and a second external partial electrode 12b that can be attached to and detached from the first external partial electrode 12a, and thus includes both external partial electrodes 12a and 12b. The external electrodes 12 are electrically connected to each other and integrated with the external electrode 12.
Further, the external electrode 12 includes a reaction chamber C having a slightly similar space that is slightly larger than the main part of the plastic molded container main body 1 on which the gas barrier thin film mainly composed of inorganic oxide is to be applied. In the drawing, for the sake of illustration, the main part of the reaction chamber C and the main part of the plastic molded container body 1 are drawn in substantially the same shape).
The internal electrode 16 is disposed in the reaction chamber C so as to be positioned at the center thereof.
Thus, the internal electrode 16 is formed of a hollow body and includes a plurality of raw material gas blowing holes 16a. Further, the internal electrode 16 is continuously provided with a raw material gas supply pipe 17 made of a conductive material. ing.
In the raw material gas supply pipe 17 connected to the internal electrode 16, as indicated by an arrow P ₂ , argon (Ar), helium (He) or the like is contained in the plastic molding container body 1 in the reaction chamber C. An inert gas is supplied.
Furthermore, the raw material gas supply pipe 17 provided continuously to the inner electrode 16, as indicated by arrow P _2, the reaction chamber plastic molded container body 1 in C, evaporation monomers such as organosilicon compounds A raw material gas composition gas for vapor deposition prepared using gas, oxygen gas, inert gas, or the like is supplied.
The internal electrode 16 is grounded via a source gas supply pipe 17.
Note that a vacuum source (not shown) is connected to the reaction chamber C via an exhaust pipe 15.
On the other hand, a high-frequency power source 14 is connected to the external electrode 12 via a matching unit 13.
A plurality of magnets 18 for generating a magnetic field in the reaction chamber C are disposed around the external electrode 12.
The external electrode 12 is supported by the base 10 via the insulating plate 1.
In the present invention, when an inert gas and a deposition source gas composition are supplied to the internal electrode 16 through the source gas supply pipe 17, the internal gas 16 is not discharged from the source gas blowing holes 16 a provided in the internal electrode 16. The active gas and the source gas composition for vapor deposition are blown out.
It is desirable that a plurality of source gas blowing holes 16 a be provided in the internal electrode 16 in order to diffuse the blown inert gas and the vapor deposition source gas composition into the reaction chamber C uniformly.
Further, the reaction chamber C is configured such that air in the reaction chamber C is exhausted by a vacuum source (vacuum pump) through an exhaust pipe 15 as indicated by an arrow P ₁ . .
Furthermore, in the present invention, the magnet 18 not only can generate a magnetic field of, for example, 875 G (87.5 mT) in the reaction chamber C to generate high-quality plasma with high density. It is possible to make plasma collide with the inner surface of the plastic molded container body 1 with acceleration, have a higher gas barrier property, and mainly consist of an inorganic oxide firmly attached to the inner surface of the plastic molded container body 1. A magnet capable of forming a gas barrier thin film is applicable.

Next, in the present invention, a method for producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus according to the present invention shown in FIG. 1 will be described.
First, in the present invention, for example, a plastic molded container body 1 including a blow molded container body made of a polyester resin is manufactured.
Next, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic molded container body 1 manufactured as described above, and are electrically connected and integrated with the external electrode 12.
Next, the inside of the reaction chamber C is evacuated to a pressure at which plasma can be generated by a vacuum pump (not shown) connected to the exhaust pipe 15 to increase the degree of vacuum.
Next, an inert gas such as argon (Ar), helium (He) or the like is supplied from the source gas supply pipe 17 into the plastic molding container main body 1 in the reaction chamber C and blown out from the source gas blowout hole 16. A high frequency voltage is applied between the electrode 12 and the internal electrode 16 to generate a high frequency glow discharge in the reaction chamber C, and a magnetic field is generated in the reaction chamber C by the magnet 18.
Next, the inert gas ejected from the raw material gas blowing holes 16 is converted into plasma in the reaction chamber C, and collides with the inner surface of the plastic molded container body 1 with acceleration. A fine uneven smooth surface is formed.
At that time, by generating a magnetic field by the magnet 18 inside the reaction chamber C, it becomes possible not only to generate high-quality and high-quality inert gas plasma, but also to plasmaize the inner surface of the plastic molded container body 1. The inert gas thus made collides with acceleration, and it becomes possible to efficiently form a fine uneven smooth surface on the inner surface of the plastic molded container body 1.
Next, the inside of the reaction chamber C is again evacuated by the vacuum pump connected to the exhaust pipe 15 until the pressure at which plasma can be generated is reached, and the degree of vacuum in the reaction chamber C is increased as described above.
Next, a source gas composition for vapor deposition prepared by using a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, or the like through a source gas supply pipe 17 in the reaction chamber C is appropriately used. Further, a high frequency voltage is applied between the external electrode 12 and the internal electrode 16 to generate a high frequency glow discharge in the reaction chamber C and a magnetic field is generated in the reaction chamber C by the magnet 18.
At this time, the vapor deposition source gas composition supplied into the reaction chamber C by the high-frequency glow discharge is subjected to a gas phase reaction in the reaction chamber C, and a reaction mainly composed of plasma-converted inorganic oxide such as silicon oxide. A product is generated, and thus the reaction product is deposited on the entire surface of the uneven smooth surface by the plasma treatment formed on the entire inner surface of the plastic molded container body 1 with acceleration.
At that time, by generating a magnetic field by the magnet 18 in the reaction chamber C, it becomes possible not only to generate a high-quality and high-quality plasma reaction product, but also to plasma the inner surface of the plastic molded container body 1. The reaction product made into plasma collides with the entire surface of the uneven surface by the treatment with acceleration, and the plasma processing of the inner surface of the plastic molded container main body 1 is efficiently performed on the entire surface of the uneven surface by plasma treatment. It is possible to deposit a gas barrier thin film made of a reaction product mainly composed of an inorganic oxide.
After passing a sufficient time to form a gas barrier thin film composed of a reaction product mainly composed of an inorganic oxide such as silicon oxide, a raw material gas for vapor deposition into the reaction chamber C through a raw material gas supply pipe 17 The supply of the composition is stopped, and then the atmosphere is introduced into the reaction chamber C.
Thereafter, a plastic container in which the gas barrier thin film 2 mainly composed of an inorganic oxide such as silicon oxide is formed on the entire inner surface of the plastic molded container body 1 through an uneven smooth surface by plasma treatment, and the present invention is taken out. The plastic container which concerns on can be manufactured.

[Embodiment 2]
Next, a second embodiment of the plastic container according to the present invention will be described.
FIG. 2 is a schematic configuration diagram showing a schematic configuration of a low-temperature plasma chemical vapor deposition apparatus according to Embodiment 2 used for manufacturing a plastic container according to the present invention.
As shown in FIG. 2 described above, the low temperature plasma chemical vapor deposition apparatus A ₁ includes an external electrode 12 and an internal electrode 16.
The external electrode 12 includes a first external partial electrode 12a and a second external partial electrode 12b that can be attached to and detached from the first external partial electrode. The external electrode 12 including both external partial electrodes 12a and 12b is: They are electrically connected to each other and integrated with the external electrode 12, and the external electrode 12 is supported by a support device (not shown).
Further, the external electrode 12 includes a reaction chamber C having a slightly similar space that is slightly larger than the main part of the plastic molded container main body 1 on which the gas barrier thin film mainly composed of inorganic oxide is to be applied. In the drawing, for the sake of illustration, the main part of the reaction chamber C and the main part of the plastic molded container body 1 are drawn in substantially the same shape).
Note that a high frequency power source 14 is connected to the external electrode 12 via a matching unit 13.
Next, the internal electrode 16 is disposed in the reaction chamber C so as to be positioned at the center thereof.
Thus, the internal electrode 16 is formed of a hollow body and includes a plurality of raw material gas blowing holes 16a. Further, the internal electrode 16 is provided with a raw material gas supply pipe 19 made of a conductive material. Yes.
The source gas supply pipe 19 is configured to be selectively connected to a vacuum source (not shown) and a source gas supply source (not shown) in a switchable manner.
The internal electrode 16 is grounded via a source gas supply pipe 19.
Further, the source gas supply pipe 19 connected to the internal electrode 16 is formed in a mandrel shape, and the rotation means of the internal electrode 16 is fixed to the source gas supply pipe 19.
The rotating means includes an O-ring mounting portion 22a, a first ring 22 and a second ring 25, which are integral with the O-ring mounting portion 22a and fixed to the source gas supply pipe 19, and between the rings 22, 25. A sprocket 24 provided integrally with both rings 22 and 25, a chain 26 engaged with the sprocket 24, and a prime mover (not shown) for driving the chain 26 are provided.
An O-ring 21 is attached to the O-ring attachment portion 22a.
Further, the inside of the O-ring attachment portion 22a is in contact with the outer end of the mouth of the plastic molded container body 1, thereby maintaining the positional relationship with the plastic molded container body 1.
Further, a bottle fixing jig 20 made of a metal body 20a and an insulator 20b is attached around the mouth of the plastic molded container body 1 so that the plastic molded container body 1 does not rotate. ing.
The O-ring 21 is brought into close contact with the bottle fixing jig 19 so that the vacuum state in the reaction chamber C is maintained.
A slip ring 26 is provided on the second ring 25 side via a bearing 27.
The low-temperature plasma chemical vapor deposition apparatus A ₁ shown in FIG. 2 is configured so that the internal electrode 16 is rotationally driven as described above, so that the internal electrode 16 rotates. It is characterized in that the source gas can be supplied uniformly over the entire circumference, and the efficiency of vapor deposition is increased by causing plasma to collide with the inner surface of the plastic molded container body 1 with acceleration.

Next, a method for producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus A ₁ shown in FIG. 2 will be described.
First, in the present invention, for example, a plastic cooked container body 1 made of a blow molded container made of a polyester resin is manufactured.
Next, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic molded container body 1 manufactured as described above, and are electrically connected and integrated with the external electrode 12.
Next, the inside of the reaction chamber C is evacuated to a pressure at which plasma can be generated by a vacuum pump (not shown) through the source gas supply pipe 19 to increase the degree of vacuum.
Next, an inert gas such as argon (Ar) or helium (He) is supplied through the source gas supply pipe 19 while rotating the internal electrode 16 by driving the prime mover and rotating the sprocket 23 into the reaction chamber C. The high-frequency glow discharge is generated in the reaction chamber C by applying a high-frequency voltage between the external electrode 12 and the internal electrode 16 at the same time.
The inert gas ejected from the rotating raw material gas blowing hole 16 is converted into plasma, and is uniformly supplied into the reaction chamber C over the entire circumference, and the internal electrode 16 rotates, whereby the plastic molding container main body 1 is rotated. The surface is made to collide with the inner surface with acceleration, and a fine uneven smooth surface is efficiently formed on the inner surface of the plastic molded container body 1 by plasma treatment.
Next, the inside of the reaction chamber C is evacuated again through the source gas supply pipe 19 by a vacuum pump until the pressure at which plasma can be generated is reached, and the degree of vacuum in the reaction chamber C is increased as described above. . Next, a raw material gas composition for vapor deposition prepared using a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, and the like through a raw material gas supply pipe 19 in the plastic molded container body 1. A source gas blowing hole 16 that rotates and moves at an appropriate flow rate is ejected into the reaction chamber C, and a high-frequency voltage is applied between the external electrode 12 and the internal electrode 16 to generate a high-frequency glow discharge in the reaction chamber C.
At this time, the raw material gas composition for vapor deposition supplied into the reaction chamber C is subjected to a gas phase reaction in the reaction chamber C by high-frequency glow discharge, and a reaction product mainly composed of plasma-generated inorganic oxide such as silicon oxide. A product is generated, and this reaction product is allowed to collide with and adhere to the entire surface of the inner surface of the plastic molded container body 1 including the uneven surface by plasma treatment with acceleration.
At that time, kinetic energy is imparted to the plasma by the rotation of the internal electrode 16, thereby improving the efficiency of the generation of the reaction product, and the plasma has an acceleration to the plasma on the inner surface of the plastic molded container body 1. The reaction is caused to collide with the entire surface including the uneven smooth surface by the treatment, and the main surface of the inner surface of the plastic molded container body 1 including the uneven smooth surface by the plasma treatment is mainly composed of plasma-converted inorganic oxide such as silicon oxide. A gas barrier thin film made of a material can be deposited.
After a sufficient time to form the gas barrier thin film, the supply of the deposition source gas composition to the reaction chamber C through the source gas supply pipe 19 is stopped, and then the atmosphere is supplied to the reaction chamber C. Introduce.
Thereafter, an inorganic oxide such as silicon oxide is mainly formed on the inner surface of the plastic molded container body 1 through an uneven smooth surface by plasma treatment, leaving a partial region of the mouth of the plastic molded container body 1. The plastic container in which the gas barrier thin film is formed can be taken out, and the plastic container according to the present invention can be manufactured.
In this container, there is a region that is not covered with a gas barrier thin film in a part of the mouth of the plastic molded container body 1, and a gas barrier packaging container is formed by attaching a gas barrier cap to the mouth. can do.

[Embodiment 3]
Next, a third embodiment of the plastic container according to the present invention will be described.
FIG. 3 is a schematic configuration diagram showing a schematic configuration of a low-temperature plasma chemical vapor deposition apparatus according to Embodiment 3 used for manufacturing a plastic container according to the present invention.
As shown in FIG. 3 described above, the low-temperature plasma chemical vapor deposition apparatus A ₂ includes an external electrode 12 and an internal electrode 16.
The external electrode 12 includes a first external partial electrode 12a and a second external partial electrode 12b that can be attached to and detached from the first external partial electrode. The external electrode 12 including both external partial electrodes 12a and 12b is: They are electrically connected to each other and integrated with the external electrode 12, and the external electrode 12 is supported by a support device (not shown).
This external electrode 12 includes a reaction chamber C having a slightly similar space slightly larger than the main part of the plastic molded container body 1 on which the thin film is to be deposited (in the drawing, for convenience of illustration, the reaction chamber C is shown). The main part and the main part of the plastic molded container main body 1 are drawn in substantially the same shape).
Note that a high frequency power source 14 is connected to the external electrode 12 via a matching unit 13. On the other hand, the internal electrode 16 is disposed in the reaction chamber C so as to be positioned at the center thereof.
The internal electrode 16 is formed of a hollow body and includes a plurality of raw material gas blowing holes 16a. The internal electrode 16 is continuously provided with a raw material gas supply pipe 17 made of a conductive material.
The source gas supply pipe 17 is connected to a source gas supply source (not shown).
Further, a vacuum source (not shown) is connected to the reaction chamber C through an exhaust pipe 15.
Further, the internal electrode 16 is grounded via the source gas supply pipe 17.
Thus, the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG.
The rotating means includes an O-ring attachment portion 28a, a first ring 28 and a second ring 31 that are integral with the O-ring attachment portion 28a and fixed to the source gas supply pipe 17, and between the rings 28, 31. A sprocket 29 integrated with both rings 28 and 31, a chain 30 engaged with the sprocket 29, and a driving vehicle (not shown) for driving the chain 30 are provided.
The O-ring 21 is attached to the O-ring attachment portion 28a.
Further, a portion for gripping the outer end of the mouth of the plastic molded container body 1 is provided inside the O-ring mounting portion 28a.
Further, a cylindrical portion 31 a is connected to the second ring 31, and the cylindrical portion 31 a is fixed to the source gas supply pipe 17.
The cylindrical portion 31 a is provided with a slip ring 32 via a bearing 27.
The low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG. 3 is configured such that the plastic molded container body 1 is rotationally driven as described above, and since the plastic molded container body 1 rotates, It is characterized in that the source gas can be supplied uniformly over the entire circumference, and that plasma is accelerated and collides with the inner surface of the plastic molded container body 1 to increase the efficiency of vapor deposition.

Next, a method for producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG. 3 will be described.
First, in the present invention, for example, a plastic molded container body 1 made of a blow molded container made of polyester resin is manufactured.
Next, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic molded container body 1 manufactured as described above, and are electrically connected and integrated with the external electrode 12.
Next, the inside of the reaction chamber C is evacuated to a pressure at which plasma can be generated by a vacuum pump (not shown) through the source gas supply pipe 17 to increase the degree of vacuum.
Next, an inert gas such as argon (Ar), helium (He), etc., is rotated in the reaction chamber C by driving the prime mover and rotating the sprocket 23 while rotating the plastic molding container body 1. 17, and is blown out from the raw material gas blowing hole 16. At the same time, a high frequency voltage is applied between the external electrode 12 and the internal electrode 16 to generate a high frequency glow discharge in the reaction chamber C.
Thus, the inert gas ejected from the rotating raw material gas blowout hole 16 is converted into plasma and uniformly supplied into the reaction chamber C over the entire circumference, and the internal electrode 16 rotates, thereby plastic molding. The container body 1 is caused to collide with the inner surface with acceleration, and a fine uneven smooth surface is efficiently formed on the inner surface of the plastic molded container body 1 by plasma treatment.
Next, the reaction chamber C is again evacuated through the source gas supply pipe 17 by a vacuum pump until the pressure at which plasma can be generated is reached, and the degree of vacuum in the reaction chamber C is increased in the same manner as described above. . Next, a raw material gas composition for vapor deposition prepared using a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, and the like through a raw material gas supply pipe 17 in the plastic molded container body 1. A source gas blowing hole 16 that rotates and moves at an appropriate flow rate is ejected into the reaction chamber C, and a high-frequency voltage is applied between the external electrode 12 and the internal electrode 16 to generate a high-frequency glow discharge in the reaction chamber C.
At this time, the vapor deposition source gas composition supplied into the reaction chamber C by the high-frequency glow discharge is subjected to a gas phase reaction in the reaction chamber C, and a reaction mainly composed of plasma-converted inorganic oxide such as silicon oxide. A product is generated, and this reaction product is allowed to collide with and adhere to the entire surface of the inner surface of the plastic molded container body 1 including a fine uneven smooth surface by plasma treatment with acceleration.
Further, at that time, the internal electrode 16 rotates to impart kinetic energy to the plasma, thereby improving the efficiency of the generation of the reaction product, and the plasma accelerates the plastic molded container body 1. It is made to collide with the entire surface including the fine irregularities smooth surface by the plasma treatment of the inner surface, and the inorganic surface such as plasma oxidized silicon oxide is efficiently applied to the entire surface including the fine irregularities smooth surface by the plasma treatment of the inner surface of the plastic molding container body 1. A gas barrier thin film made of a reaction product mainly composed of oxide can be deposited.
After a sufficient time for forming the gas barrier thin film, the supply of the deposition source gas composition to the reaction chamber C via the source gas supply pipe 17 is stopped, and then the atmosphere is supplied to the reaction chamber C. Introduce.
Thereafter, a plastic container in which a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the inner surface of the plastic molded container body 1 through a fine uneven smooth surface by plasma processing is taken out, and the present invention is applied. Such a plastic container can be manufactured.
In this container, there is a region that is not covered with the gas barrier thin film at a part of the mouth of the plastic molded container body 1, but the gas barrier packaging container is attached to the mouth by wearing a gas barrier cap. Can be configured.

[Embodiment 4]
Next, a fourth embodiment of the plastic container according to the present invention will be described.
FIG. 4 is a schematic configuration diagram showing a schematic configuration of a low-temperature plasma chemical vapor deposition apparatus according to Embodiment 4 used for manufacturing a plastic container according to the present invention.
As shown in FIG. 4, the low temperature plasma chemical vapor deposition apparatus A ₃ is provided with a magnet 18 around the external electrode 12 of the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG. In other respects, the configuration is the same as that of the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG.
Thus, as the magnet 18, not only can a magnetic field of, for example, 875 G (87.5 mT) be generated in the reaction chamber C to generate high-quality high-quality plasma, but also plastic. It is possible to cause plasma to collide with the inner surface of the molded container body 1 with acceleration, to have higher gas barrier properties, and to the inner surface of the plastic molded container body 1, an uneven smooth surface by plasma treatment, and tough A magnet capable of forming a gas barrier thin film deposited on the substrate can be applied.
Other configurations are the same as the configuration of the low-temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG.
As described above, the low-temperature plasma chemical vapor deposition apparatus A ₃ shown in FIG. 4 generates a magnetic field of, for example, 875 G (87.5 mT) in the reaction chamber C by the magnet 18 to generate high-quality high-quality plasma. In addition to making it possible to generate, the internal electrode 16 is configured to be driven to rotate, and since the internal electrode 16 rotates, the source gas can be supplied uniformly over the entire circumference. In addition, the plasma is caused to collide with the inner surface of the plastic molding container body 1 with acceleration to increase the efficiency of plasma processing and vapor deposition.

Next, a method for producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus A ₃ of the present invention shown in FIG. 4 will be described.
First, in the present invention, for example, a plastic molded container body 1 made of a blow molded container made of polyester resin is manufactured.
Next, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic molded container body 1 manufactured as described above, and are electrically connected and integrated with the external electrode 12.
Next, the inside of the reaction chamber C is evacuated to a pressure at which plasma can be generated by a vacuum pump (not shown) through the source gas supply pipe 19 to increase the degree of vacuum.
Next, an inert gas such as argon (Ar) or helium (He) is passed through the source gas supply pipe 19 while the internal electrode 16 is rotated by driving the prime mover in the reaction chamber C and rotating the sprocket 23. The high-frequency voltage is applied between the external electrode 12 and the internal electrode 16 to generate a high-frequency glow discharge in the reaction chamber C and a magnetic field is generated in the reaction chamber C by the magnet 18. Let
The inert gas spouted from the raw material gas blowout hole 16 rotating and moving as described above is converted into plasma and uniformly supplied into the reaction chamber C over the entire circumference, and the internal electrode 16 rotates, whereby the plastic molding container main body is rotated. 1 is made to collide with the inner surface of the plastic molding body 1 with acceleration, and a fine uneven smooth surface is efficiently formed on the inner surface of the plastic molded container body 1.
At that time, by generating a magnetic field by the magnet 18 inside the reaction chamber C, it becomes possible not only to generate high-quality and high-quality inert gas plasma, but also to plasmaize the inner surface of the plastic molded container body 1. The inert gas thus made is allowed to collide with acceleration, and a fine uneven smooth surface can be efficiently formed on the inner surface of the plastic molded container body 1 by plasma treatment.
Next, the inside of the reaction chamber C is evacuated again through the source gas supply pipe 19 by a vacuum pump until the pressure at which plasma can be generated is reached, and the degree of vacuum in the reaction chamber C is increased as described above. . Next, a raw material gas composition for vapor deposition prepared using a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, and the like through a raw material gas supply pipe 19 in the plastic molded container body 1. The material gas is blown into the reaction chamber C from the raw material gas blowing hole 16 that rotates and moves at an appropriate flow rate, and a high frequency voltage is applied between the external electrode 12 and the internal electrode 16 to generate a high frequency glow discharge in the reaction chamber C. .
At this time, the vapor deposition source gas composition supplied into the reaction chamber C by the high-frequency glow discharge is subjected to a gas phase reaction in the reaction chamber C, and a reaction mainly composed of plasma-converted inorganic oxide such as silicon oxide. A product is generated, and this reaction product is allowed to collide with and adhere to the entire surface of the inner surface of the plastic molded container body 1 including a fine uneven smooth surface by plasma treatment.
At that time, it is possible not only to generate a high-quality and high-quality plasma reaction product by generating a magnetic field by the magnet 18 in the reaction chamber C, but also to generate plasma by rotating the internal electrode 16. Kinetic energy is applied to the inner surface of the plastic molding container main body 1 and the entire surface including the fine uneven smooth surface by the plasma treatment is made to collide with the plasma reaction product with acceleration, and the plastic molding container main body 1 is efficiently made. It is possible to deposit a gas barrier thin film made of a reaction product mainly composed of an inorganic oxide such as silicon oxide formed into plasma on the entire surface including a fine uneven smooth surface by plasma treatment of the inner surface of the substrate.
Thus, after a sufficient time to form the gas barrier thin film, the supply of the deposition source gas composition to the reaction chamber C via the source gas supply pipe 19 is stopped, and then the reaction chamber Introduce air to C.
Thereafter, a plastic container in which a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the inner surface of the plastic molded container body 1 through a fine uneven smooth surface by plasma processing is taken out, and the present invention is applied. Such a plastic container can be manufactured.
In this container, there is a region that is not covered with the gas barrier thin film at a part of the mouth of the plastic molded container body 1, but the gas barrier packaging container is attached to the mouth by wearing a gas barrier cap. Can be configured.

[Embodiment 5]
Next, a fifth embodiment of the plastic container according to the present invention will be described.
FIG. 5 is a schematic configuration diagram showing a schematic configuration of a low-temperature plasma chemical vapor deposition apparatus according to Embodiment 5 used for manufacturing a plastic container according to the present invention.
As shown in FIG. 5, the low temperature plasma chemical vapor deposition apparatus A ₄ is provided with a magnet 18 around the external electrode 12 of the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG. Other configurations are the same as those of the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG.
In the low-temperature plasma chemical vapor deposition apparatus A ₄ shown in FIG. 5, as the magnet 18, for example, a magnetic field of 875 G (87.5 mT) is generated in the reaction chamber C to generate high-quality high-quality plasma. In addition, it is possible to cause plasma to collide with the inner surface of the plastic molded container body 1 with acceleration, to have a higher gas barrier property, and also to the blow molded container body 1 made of polyester resin. A magnet capable of forming a gas barrier thin film firmly adhered to the inner surface can be applied.
The other configuration is the same as that of the low temperature plasma chemical vapor deposition apparatus A ₂ shown in FIG.
As described above, the low-temperature plasma chemical vapor deposition apparatus A ₄ shown in FIG. 5 generates a magnetic field of, for example, 875 G (87.5 mT) in the reaction chamber C by the magnet 18 to generate high-quality high-quality plasma. In addition to making it possible to generate, the plastic molded container body 1 is configured to be rotationally driven, and the plastic molded container body 1 rotates so that the source gas is uniformly supplied over the entire circumference. It is possible to increase the efficiency of vapor deposition by causing the plasma to collide with the inner surface of the plastic molded container body 1 with acceleration.

Next, a method for producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus A ₄ of the present invention shown in FIG. 5 will be described.
First, in the present invention, for example, a plastic molded container body 1 made of a blow molded container made of polyester resin is manufactured.
Next, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic molded container body 1 manufactured as described above, and are electrically connected and integrated with the external electrode 12.
Next, the inside of the reaction chamber C is evacuated to a pressure at which plasma can be generated by a vacuum pump (not shown) through the source gas supply pipe 19 to increase the degree of vacuum.
Next, an inert gas such as argon (Ar), helium (He), or the like is rotated into the reaction chamber C while the plastic molding container body 1 is rotated by driving the prime mover and rotating the sprocket 29. The high-frequency voltage is applied between the external electrode 12 and the internal electrode 16 at the same time to generate a high-frequency glow discharge in the reaction chamber C and the magnet 18 in the reaction chamber C. To generate a magnetic field.
The inert gas spouted from the raw material gas blowout hole 16 that rotates as described above is converted into plasma, supplied into the reaction chamber C, and the plastic molding container body 1 is rotated by rotating the plastic molding container body 1. 1 is made to collide with the inner surface of 1 uniformly in the circumferential direction, and a fine uneven smooth surface is efficiently formed on the inner surface of the plastic molded container body 1 by plasma treatment.
At that time, by generating a magnetic field by the magnet 18 inside the reaction chamber C, it becomes possible not only to generate high-quality and high-quality inert gas plasma, but also to plasmaize the inner surface of the plastic molded container body 1. The inert gas thus made is allowed to collide with acceleration, and a fine uneven smooth surface can be efficiently formed on the inner surface of the plastic molded container body 1 by plasma treatment.
Next, the inside of the reaction chamber C is again evacuated through the exhaust pipe 15 by a vacuum pump until the pressure at which plasma can be generated is reached, and the degree of vacuum in the reaction chamber C is increased as described above.
Next, a raw material gas composition for vapor deposition prepared using a monomer gas for vapor deposition such as an organosilicon compound, oxygen gas, inert gas, and the like through a raw material gas supply pipe 17 in the plastic molded container body 1. A high frequency voltage is applied between the external electrode 12 and the internal electrode 16 in a state in which a magnetic field is generated by the magnet 18 in the reaction chamber from the source gas blowing hole 16 that rotates and moves at an appropriate flow rate. Applied to generate a high-frequency glow discharge in the reaction chamber C.
At this time, the vapor deposition source gas composition supplied into the reaction chamber C by the high-frequency glow discharge is subjected to a gas phase reaction in the reaction chamber C, and a reaction mainly composed of plasma-converted inorganic oxide such as silicon oxide. A product is generated, and this reaction product is made to collide with and adhere to the entire surface including a fine uneven smooth surface by plasma treatment of the inner surface of the plastic molded container body 1 rotating with acceleration.
At that time, it is possible not only to generate a high-quality and high-quality plasma reaction product by generating a magnetic field by the magnet 18 in the reaction chamber C, but also to generate plasma by rotating the internal electrode 16. Kinetic energy is applied to the inner surface of the plastic molded container body 1 and the reaction product formed into a plasma is collided with acceleration on the entire surface of the inner surface of the plastic molded container body 1 including the fine uneven surface by plasma treatment. It is possible to deposit a gas barrier thin film made of a reaction product mainly composed of an inorganic oxide such as silicon oxide formed into plasma on the entire surface including a fine uneven smooth surface by the plasma treatment.
Next, after a sufficient time for forming the gas barrier thin film, the supply of the deposition source gas composition to the reaction chamber C through the source gas supply pipe 19 is stopped, and then the reaction chamber C is supplied to the reaction chamber C. Introduce air.
Thereafter, a plastic container in which a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the inner surface of the plastic molded container body 1 through a fine uneven smooth surface by plasma processing is taken out, and the present invention is applied. Such a plastic container can be manufactured.
In this container, there is a region that is not covered with the gas barrier thin film at a part of the mouth of the plastic molded container body 1, but the gas barrier packaging container is attached to the mouth by wearing a gas barrier cap. Can be configured.
The illustrations of the above embodiments 1 to 5 illustrate several examples of the plastic container according to the present invention, and the present invention is not limited to the above embodiments 1 to 5. .

As is apparent from the above description, as shown in FIG. 6, the present invention uses a low-temperature plasma chemical vapor deposition apparatus as described above, and uses a plastic molded container body 1 on which a thin film is to be deposited in an external electrode. Place the internal electrode in the plastic molding container body 1, apply a high frequency voltage between the electrodes, and plastic molding with the acceleration of the magnetic field lines and / or rotation of the internal electrode or the plastic molding container body 1 The concave / convex smooth surface 2 formed by the plasma treatment of the inner surface of the plastic molded container main body 1 by the high-frequency glow discharge decomposition of the reactive gas in the reaction chamber together with the formation of the concave / convex smooth surface 2 by the plasma treatment by colliding with the inner surface of the container main body 1. A plastic film according to the present invention comprising a gas barrier thin film 3 mainly composed of an inorganic oxide such as silicon oxide. It is capable of producing a manufactured container B.
The plastic container according to the present invention causes the plasma to collide with the inner surface of the plastic molded container body with acceleration due to the lines of magnetic force and / or rotation of the internal electrodes or the plastic molded container body, and the uneven surface 2 by plasma treatment under reduced pressure. And a gas barrier thin film 3 that is firmly fixed to the inner surface of the plastic molded container body by high-frequency glow discharge decomposition of the reactive gas in the reaction chamber through the uneven smooth surface 2 by the plasma treatment, and has a high gas barrier property. The gas barrier thin film 3 is firmly fixed to the inner surface of the plastic molded container body and does not peel off.

In the low-temperature plasma chemical vapor deposition apparatus as described above, the inside of the reaction chamber C is decompressed by a vacuum pump, and the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ It is desirable to prepare at ˜1 × 10 ⁻⁷ Torr position.
Further, a vapor deposition monomer such as an organic silicon compound as a raw material is volatilized using a raw material volatilization supply device (not shown) or the like.
The vaporized evaporation monomer is mixed with oxygen gas, inert gas, or the like supplied from another gas supply device (not shown) to prepare a vapor deposition source gas composition.
The vapor deposition source gas composition thus obtained is introduced into the reaction chamber C via the source gas supply pipe 17.
In this case, the content of the vapor deposition monomer gas such as the vapor deposition raw material gas composition is about 1 to 40%, the oxygen gas content is about 10 to 70%, and the inert gas content is 10 to 10%. For example, the mixing ratio of the vapor deposition monomer gas such as an organosilicon compound, the oxygen gas, and the inert gas is preferably about 1: 6: 5 to 1:17:14. desirable.

The degree of vacuum in the reaction chamber C when the vapor deposition source gas composition supplied into the reaction chamber C is caused to undergo a gas phase reaction in the reaction chamber C by high-frequency glow discharge is 1 × 10 ⁻¹ to It is desirable that the degree of vacuum is adjusted to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr, and the time for forming the gas barrier thin film is about 1 to 300 seconds, Preferably, it is desirable to adjust to about 3 to 20 seconds.
In the low-temperature plasma chemical vapor deposition apparatus described above, the formation of the gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is performed on the entire surface including the uneven smooth surface by the plasma treatment of the inner surface of the plastic molded container body. It is formed into a thin film in the form of SiO _X while the phased feed gas is oxidized with oxygen gas.
Therefore, the formed gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible.
Accordingly, the gas barrier property of a thin film mainly composed of an inorganic oxide such as silicon oxide is much higher than that of a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method. Thus, a sufficient gas barrier property can be obtained with a thin film thickness.

In the present invention, the inner surface of the plastic molded container body 1 is cleaned by the SiO _x plasma, and polar groups, free radicals, etc. are generated on the inner surface of the plastic molded container body. This has the advantage that the adhesion between the gas barrier thin film mainly composed of an inorganic oxide such as the inner surface of the plastic molded container body is high.
Further, the degree of vacuum in the reaction chamber C when forming a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide as described above is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × Since the pressure is adjusted to 10 ⁻¹ to 1 × 10 ⁻³ Torr, the degree of vacuum when forming a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method is 1 × 10 ^−4. ˜1 × 10 ⁻⁵ Torr level is lower than the vacuum level, so the vacuum setting time when the plastic molded container body is replaced (the predetermined vacuum degree after the plastic molded container body is placed in the reaction chamber C) The time required for the adjustment can be shortened.
Therefore, a stable degree of vacuum can be easily obtained, and the film forming process is stabilized.

In the present invention, a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide formed by using a vapor deposition monomer gas such as an organosilicon compound has a chemical reaction between a vapor deposition monomer gas such as an organosilicon compound and oxygen gas. A gas phase reaction is performed, and the reaction product is deposited on the entire inner surface of the plastic molded container body to form a dense and flexible thin film.
This thin film is usually a continuous thin film mainly composed of silicon oxide represented by the general formula SiO _x (where X represents a number from 0 to 2).
Thus, the gas barrier thin film mainly composed of silicon oxide has the general formula SiO _x (where X represents a number of 1.3 to 1.9) in terms of transparency and gas barrier properties. A thin film mainly composed of silicon oxide is preferable.
The value of X in the above general formula varies depending on the molar ratio of vapor deposition monomer gas to oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself Yellowish and poor transparency.
The gas barrier thin film mainly composed of silicon oxide is composed of a gas barrier thin film mainly composed of silicon oxide containing at least silicon atoms, oxygen atoms, and carbon atoms by chemical bonding.

More specifically, the gas barrier thin film mainly composed of silicon oxide is composed mainly of silicon oxide, and at least one of compounds composed of carbon, hydrogen, silicon or oxygen, or two or more elements thereof. It is characterized by comprising a continuous thin film whose type is contained by chemical bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by chemical bonds.
Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.
Furthermore, by changing the conditions of the vapor deposition process, the type and amount of the compound contained in the gas barrier thin film mainly composed of silicon oxide can be changed.

Therefore, the content of the compound contained in the gas barrier thin film mainly composed of silicon oxide is about 0.1 to 50%, preferably about 5 to 20%.
If the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the gas barrier thin film mainly composed of silicon oxide will be insufficient, and scratches, cracks, etc. will occur due to bending stress. It is difficult to stably maintain a high gas barrier property, and if it exceeds 50%, the gas barrier property is lowered, which is not preferable.
Furthermore, in the present invention, in the gas barrier thin film mainly composed of silicon oxide, the content of the compound contained in the gas barrier thin film mainly composed of silicon oxide is determined based on the surface of the gas barrier thin film mainly composed of silicon oxide. It is preferable to increase from 1 to the depth direction of the thin film. With this configuration, on the surface of the gas barrier thin film mainly composed of silicon oxide, the impact resistance and the like are enhanced by the compound contained in the gas barrier thin film mainly composed of silicon oxide. Since the content of the compound contained in the gas barrier thin film mainly composed of silicon oxide is large at the interface with the inner surface of the plastic molded container main body, the gas thin film with respect to the inner surface of the plastic molded container main body Is that the adhesion of
In the present invention, at least the silicon atom, oxygen atom, and carbon atom are chemically bonded to the gas barrier thin film mainly composed of the inorganic oxide, and the carbon atom weight is 80 to 130% with respect to 100 silicon atom weight. This is a gas barrier thin film mainly composed of silicon oxide.

  Furthermore, in the present invention, the gas barrier thin film mainly composed of the above inorganic oxide has at least silicon atoms, oxygen atoms, and carbon atoms bonded thereto, and further has a carbon atom weight of 80 to 100 silicon atoms. The ratio is 130%, and the shrinkage ratio of the surface area of the plastic molded container body immediately after molding of the plastic molded container body is 3%. It consists of a gas barrier thin film mainly composed of silicon oxide that can follow the shrinkage and expansion of the film.

  Thus, in the present invention, for the gas barrier thin film mainly composed of silicon oxide, for example, an X-ray electron spectrometer (Xray Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS) The above physical properties are confirmed by analyzing a gas barrier thin film mainly composed of silicon oxide by using a surface analysis apparatus such as ion etching in the depth direction and the like. be able to.

In the present invention, the thickness of the gas barrier thin film mainly composed of silicon oxide is preferably about 50 to 4000 mm. Specifically, the film thickness is about 60 to 1000 mm. Is desirable.
Thus, if the gas barrier thin film is thicker than 1000 mm or even 4000 mm, it is not preferable because cracks and the like are likely to occur in the film.
On the other hand, if it is 60 mm or less than 50 mm, it is difficult to achieve the gas barrier effect.
The film thickness can be measured, for example, by a fundamental parameter method using a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation.
Further, changing the film thickness of the gas barrier thin film mainly composed of silicon oxide increases the deposition acceleration of the gas barrier thin film mainly composed of silicon oxide (thin film growth thickness per unit time). That is, it can be carried out by increasing the monomer gas and oxygen gas amounts, increasing the deposition time, or the like.

Next, examples of vapor deposition monomers such as organic silicon compounds for forming a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide include 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane. , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Organosilicon compounds such as methoxysilane, methyltriethoxysilane, octamethylcyclosiloxane, etc. can be used.
Among the organosilicon compounds described above, 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane is used as a raw material because of its handleability, the characteristics of the formed continuous thin film, etc. Particularly preferred.
Moreover, as an inert gas, argon gas, helium gas, etc. can be used, for example.
Furthermore, in the present invention, the vapor deposition raw material gas composition prepared using the above-described monomer gas for vapor deposition, such as an organosilicon compound, oxygen gas, inert gas, etc. contains, for example, carbon atoms. As a supply source to be supplied, for example, methane gas, propane gas, carbon dioxide, acetylene gas, or other gas can be added. Thus, by adding these, flexibility can be imparted to the gas barrier thin film mainly composed of inorganic oxide.

Next, as the plastic molded container body constituting the plastic container according to the present invention, for example, polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and others Blow-molded containers can be used.
Further, in the present invention, basically, for example, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyacryl or polymethacryl resin, polyacryl resin, polystyrene resin, styrene-butadiene-acrylonitrile. One or more types of copolymers, polycarbonate resins, polyamide resins, polyacetal resins, and other resins are used as molding resin raw materials, and these resins can be used for, for example, extrusion molding, injection molding, blow molding, It is possible to use a plastic molded container body formed of a molded container of a bottle shape, a cup shape, a bowl shape, or other shapes formed by cast molding, thermoforming, or other molding methods.

  Thus, as a plastic molded container body constituting the plastic container according to the present invention, a blow molded container made of a polyester resin suitable for filling and packaging liquid beverages, seasonings, liquor, beer, and other liquid materials, Alternatively, it is desirable to use a blow molded container made of a polyolefin resin such as a polyethylene resin or a polypropylene resin.

Furthermore, in the present invention, as the plastic molded container body, it is preferable to prepare a moisture content by a drying means or the like and use a plastic molded container body having a low moisture content.
Thus, in the present invention, the moisture content can be adjusted by a method comprising, for example, heat drying, vacuum drying, or a combination of heat drying and vacuum drying. .
Thus, in the present invention, when the plastic molded container body is allowed to stand at room temperature after molding, the water content is about 4000 ppm, and the water content is adjusted to about 3000 ppm or less. When a gas barrier thin film mainly composed of an inorganic oxide is laminated using a phase growth apparatus, an effect of improving the gas barrier property is recognized, and further, the moisture content is reduced to about 700 ppm, and the above low temperature is reduced. When a gas barrier thin film composed mainly of an inorganic oxide is laminated using a plasma chemical vapor deposition apparatus, the gas barrier effect is maximized, and the gas barrier effect remains flat even if the moisture content is lowered thereafter. It was to become.
The plastic molded container body has a water content of about 2000 ppm immediately after blow molding, and therefore, in-line after blow molding, using the above-mentioned low temperature plasma chemical vapor deposition apparatus, inorganic oxidation is performed. By laminating a gas barrier thin film mainly composed of an object, it is possible to manufacture a plastic container according to the present invention having a high gas barrier effect, and thereby a drying process for adjusting the moisture content of the plastic molded container body, etc. It has the advantage that the plastic container according to the present invention having a high gas barrier effect can be produced without passing through, that is, by shortening the process.
In the present invention, the moisture content of the plastic molded container main body can be measured by, for example, a trace moisture meter or the like.

Next, in the present invention, the unevenness smooth surface by plasma treatment provided on the entire inner surface of the plastic molded container main body is formed with fine irregularities on the inner surface of the plastic molded container body by plasma treatment, and the uneven surface Therefore, as the smoothness of the fine uneven surface, for example, the center line average roughness Ra (μm) is about 0.01 <Ra <0.05. It is preferable to be within the range.
In the present invention, the smoothness of the fine uneven smooth surface by the plasma treatment can be measured by, for example, a surface roughness meter or the like.
Next, the present invention will be described in more detail with reference to examples.

Example 1 is an example of producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus shown in FIG.
First, polyethylene terephthalate resin is used as a molding material. First, in accordance with a conventional method, this is injection molded to form a preform, and then this preform is blow molded to blow a polyethylene terephthalate resin having a size of 500 ml. Molded bottles were produced.
Next, the polyethylene terephthalate resin blow-molded bottle produced above was dried for 24 hours using a vacuum oven [TABAI ESPEC Co., Ltd., model name, VACUUM OPEN: LCV-232], When the moisture content was measured with a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000), the moisture content in the blow molded bottle made of polyethylene terephthalate resin was reduced from 4000 ppm to 700 ppm. .
Next, the polyethylene terephthalate resin blow-molded bottle having the water content adjusted to 700 ppm was mounted on the low temperature plasma chemical vapor deposition apparatus shown in FIG. 1, and then the reaction chamber was vacuumed by a vacuum pump to 0.06 Torr ( It was lowered to 8.0 Pa).
Next, as a pretreatment of the inner surface of the blow molded bottle, argon gas is used, supplied into the reaction chamber, and a magnetic field of 875 G is formed in the reaction chamber by a magnet arranged around the external electrode. A high frequency voltage of 13.56 MHz and 300 W was applied between the electrodes to generate plasma, and this state was maintained for about 20 seconds.
By performing this pretreatment, the surface of the inner surface of the blow molded bottle formed a fine uneven smooth surface, and the smoothness was Ra = 0.03.
Next, again, the pressure in the reaction chamber is reduced to 0.06 Torr by a vacuum pump, and a magnetic field of 875 G is formed in the reaction chamber by a magnet arranged around the external electrode, and 13. A high frequency voltage of 56 MHz and 300 W was applied, and then a raw material gas composition consisting of hexamethyldisiloxane: oxygen gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min. did.
Next, while generating the plasma of the raw material gas, it is held for about 30 seconds under the state where the plasma is generated, and the inner surface of the blow molded bottle is made of a vapor deposition film mainly composed of silicon oxide having a thickness of about 1200 mm. A plastic container according to the present invention was produced in which a gas barrier thin film was formed and then contracted due to the influence of internal stress remaining after molding.

Example 2 is an example of producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus shown in FIG.
First, a polyethylene terephthalate resin is used as a molding material, and a preform is formed by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is molded. Manufactured.
Next, the polyethylene terephthalate resin blow-molded bottle produced above was dried for 24 hours using a vacuum oven [TABAI ESPEC Co., Ltd., model name, VACUUM OVEN: LCV-232], When the moisture content was measured with a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000), the moisture content in the blow molded bottle made of polyethylene terephthalate resin was reduced from 4000 ppm to 700 ppm. .
Next, the polyethylene terephthalate resin blow-molded bottle having the water content adjusted to 700 ppm was mounted on the low temperature plasma chemical vapor deposition apparatus shown in FIG. 2, and then the reaction chamber was vacuumed by a vacuum pump of 0.06 Torr ( It was lowered to 8.0 Pa).
Next, as pretreatment of the inner surface of the blow-molded bottle, argon gas is used, and this is supplied into the reaction chamber, and a high-frequency voltage of 13.56 MHz and 300 W is applied between the electrodes while rotating the internal electrodes. Was generated and maintained for about 20 seconds.
By performing this pretreatment, the surface of the inner surface of the blow molded bottle uniformly formed a fine uneven smooth surface, and the smoothness was Ra = 0.03.
Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr with a vacuum pump, a high frequency voltage of 13.56 MHz and 300 W is applied between the electrodes while rotating the internal electrodes, and then hexamethyldisiloxane: oxygen A raw material gas composition consisting of gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 30 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A gas-barrier thin film consisting of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide was formed, and then a plastic container according to the present invention was contracted due to the influence of internal stress remaining after molding.

Example 3 is an example of manufacturing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus shown in FIG.
First, a polyethylene terephthalate resin is used as a molding material, and a preform is molded by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is formed. Manufactured.
Next, the polyethylene terephthalate resin blow-molded bottle produced above was dried for 24 hours using a vacuum oven [TABAI ESPEC Co., Ltd., model name, VACUUM OVEN: LCV-232], When the moisture content was measured with a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000), the moisture content in the blow molded bottle made of polyethylene terephthalate resin was reduced from 4000 ppm to 700 ppm. .
Next, the polyethylene terephthalate resin blow-molded bottle having the water content adjusted to 700 ppm was mounted on the low-temperature plasma chemical vapor deposition apparatus shown in FIG. 3, and the vacuum inside the reaction chamber was then adjusted to 0.06 Torr ( It was lowered to 8.0 Pa).
Next, as a pretreatment of the inner surface of the blow molded bottle, argon gas is used, supplied into the reaction chamber, and a high frequency of 13.56 MHz and 300 W is provided between the electrodes while rotating the blow molded bottle made of polyethylene terephthalate resin. A voltage was applied to generate plasma, and this state was maintained for about 20 seconds.
By performing this pretreatment, the surface of the inner surface of the blow molded bottle uniformly formed a fine uneven smooth surface, and the smoothness was Ra = 0.03.
Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr with a vacuum pump, a high frequency voltage of 13.56 MHz and 300 W is applied between the electrodes while rotating the internal electrodes, and then hexamethyldisiloxane: oxygen A raw material gas composition consisting of gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 30 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A gas-barrier thin film consisting of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide was formed, and then a plastic container according to the present invention was contracted due to the influence of internal stress remaining after molding.

Example 4 is an example of producing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus shown in FIG.
First, a polyethylene terephthalate resin is used as a molding material, and a preform is molded by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is formed. Manufactured.
Next, the polyethylene terephthalate resin blow-molded bottle produced above was dried for 24 hours using a vacuum oven [TABAI ESPEC Co., Ltd., model name, VACUUM OPEN: LCV-232], When the moisture content was measured with a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000), the moisture content in the blow molded bottle made of polyethylene terephthalate resin was reduced from 4000 ppm to 700 ppm. .
Next, the polyethylene terephthalate resin blow-molded bottle whose water content was adjusted to 700 ppm was mounted on the low-temperature plasma chemical vapor deposition apparatus shown in FIG. 4, and the reaction chamber was vacuum-controlled by a vacuum pump at 0.06 Torr ( It was lowered to 8.0 Pa).
Next, as a pretreatment of the inner surface of the blow-molded bottle, argon gas is used, supplied to the reaction chamber, a magnetic field is generated inside the reaction chamber by a magnet, and the internal electrodes are rotated between the electrodes 13. A plasma was generated by applying a high frequency voltage of .56 MHz and 300 W, and this state was maintained for about 20 seconds.
By performing this pretreatment, the surface of the inner surface of the blow-molded bottle uniformly formed a fine uneven smooth surface, and the smoothness was Ra = 0.025.
Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr with a vacuum pump, a high frequency voltage of 13.56 MHz and 300 W is applied between the electrodes while rotating the internal electrodes, and then hexamethyldisiloxane: oxygen A raw material gas composition consisting of gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 30 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A gas-barrier thin film consisting of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide was formed, and then a plastic container according to the present invention was contracted due to the influence of internal stress remaining after molding.

Example 5 is an example of manufacturing a plastic container according to the present invention using the low temperature plasma chemical vapor deposition apparatus shown in FIG.
First, a polyethylene terephthalate resin is used as a molding material, and a preform is molded by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is formed. Manufactured.
Next, the polyethylene terephthalate resin blow-molded bottle produced above was dried for 24 hours using a vacuum oven [TABAI ESPEC Co., Ltd., model name, VACUUM OPEN: LCV-232], When the moisture content was measured with a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000), the moisture content in the blow molded bottle made of polyethylene terephthalate resin was reduced from 4000 ppm to 700 ppm. .
Next, the polyethylene terephthalate resin blow-molded bottle having the water content adjusted to 700 ppm was mounted on the low temperature plasma chemical vapor deposition apparatus shown in FIG. 5, and then the reaction chamber was vacuumed by a vacuum pump to 0.06 Torr ( It was lowered to 8.0 Pa).
Next, as a pretreatment of the inner surface of the blow molded bottle, argon gas is used, supplied to the reaction chamber, a magnetic field is generated inside the reaction chamber by a magnet, and the polyethylene terephthalate resin blow molded container is rotated. While the plasma was generated by applying a high frequency voltage of 13.56 MHz and 300 W between the electrodes, the state was maintained for about 20 seconds.
By performing this pretreatment, the surface of the inner surface of the blow-molded bottle uniformly formed a fine uneven smooth surface, and the smoothness was Ra = 0.025.
Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr with a vacuum pump, and a high frequency voltage of 13.56 MHz and 300 W is applied between the electrodes while rotating the blow molded container made of polyethylene terephthalate resin. A raw material gas composition composed of methyldisiloxane: oxygen gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 30 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A gas-barrier thin film consisting of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide was formed, and then a plastic container according to the present invention was contracted due to the influence of internal stress remaining after molding.

Example 6 is an example in which the plastic container according to the present invention is manufactured using the low temperature plasma chemical vapor deposition apparatus shown in FIG.
First, a polyethylene terephthalate resin is used as a molding material, and a preform is molded by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is formed. Manufactured.
Next, the blow bottle formed of polyethylene terephthalate resin manufactured as described above was mounted on the low temperature plasma chemical vapor deposition apparatus shown in FIG. 4, and then the degree of vacuum was 0.06 Torr (8.0 Pa) with a vacuum pump in the reaction chamber. Lowered.
Next, as a pretreatment of the inner surface of the blow-molded bottle, argon gas is used, supplied to the reaction chamber, a magnetic field is generated inside the reaction chamber by a magnet, and the internal electrodes are rotated between the electrodes 13. A plasma was generated by applying a high frequency voltage of .56 MHz and 400 W, and this state was maintained for about 5 seconds.
By performing this pretreatment, the surface of the inner surface of the blow-molded bottle uniformly formed a fine uneven smooth surface, and the smoothness was Ra = 0.030.
Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr by a vacuum pump, a high frequency voltage of 13.56 MHz and 350 W is applied between the electrodes while rotating the internal electrodes, and then hexamethyldisiloxane: oxygen A raw material gas composition consisting of gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 20 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A plastic container according to the present invention was manufactured by forming a gas barrier thin film consisting of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide.

First, a polyethylene terephthalate resin is used as a molding material, and a preform is molded by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is formed. Manufactured.
Next, the moisture content of the blow molded bottle made of polyethylene terephthalate resin immediately after molding was measured using a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000). However, the water content in the blow molded bottle made of polyethylene terephthalate resin was 2000 ppm.
Next, the polyethylene terephthalate resin blow-molded bottle immediately after molding with a moisture content of 2000 ppm was mounted on the low-temperature plasma chemical vapor deposition apparatus shown in FIG. The degree of vacuum was reduced to 0.06 Torr (8.0 Pa) by a vacuum pump.
Next, as a pretreatment of the inner surface of the blow-molded bottle, argon gas is used, supplied to the reaction chamber, a magnetic field is generated inside the reaction chamber by a magnet, and the internal electrodes are rotated between the electrodes 13. A plasma was generated by applying a high frequency voltage of .56 MHz and 400 W, and this state was maintained for about 5 seconds.
By performing this pretreatment, the surface of the inner surface of the blow-molded bottle uniformly formed a fine uneven smooth surface, and the smoothness was Ra = 0.030.
Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr by a vacuum pump, a high frequency voltage of 13.56 MHz and 350 W is applied between the electrodes while rotating the internal electrodes, and then hexamethyldisiloxane: oxygen A raw material gas composition consisting of gas: argon gas = 1: 3: 3 (slm) was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 20 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A plastic container according to the present invention was manufactured by forming a gas barrier thin film consisting of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide.

[Comparative Example 1]
First, a polyethylene terephthalate resin is used as a molding material, and a preform is molded by injection molding according to a conventional method. Then, the preform is blow-molded, and a 500-ml polyethylene terephthalate resin blow-molded bottle is formed. Manufactured.
Next, when the polyethylene terephthalate resin blow molded bottle was left standing, the moisture content was measured using a moisture content measuring device (manufactured by Chino Co., Ltd., model name, precision trace moisture meter, CZA-3000). The water content in the blow molded bottle made of polyethylene terephthalate resin was 4300 ppm.
Next, the polyethylene terephthalate resin blow-molded bottle having a moisture content of 4300 ppm was mounted on the low-temperature plasma chemical vapor deposition apparatus shown in FIG. 4 connected inline to the molding machine, and then the reaction chamber was vacuum pumped. The degree of vacuum was lowered to 0.06 Torr (8.0 Pa).
Next, a high frequency voltage of 13.56 MHz and 350 W is applied between the electrodes while rotating the internal electrodes, and then a raw material gas composition composed of hexamethyldisiloxane: oxygen gas: argon gas = 1: 3: 3 (slm) The product was supplied while adjusting the gas flow rate to 35 ml / min.
Next, while generating the plasma of the raw material gas, it is held for about 20 seconds under the state in which the plasma is generated, leaving a partial region of the mouth of the blow molded bottle, A gas-barrier thin film made of a vapor-deposited film mainly composed of about 1200 mm of silicon oxide was formed to produce a plastic container.

[Comparative Example 2]
In the above comparative example 1, instead of setting the output of the high frequency power source at the time of vapor deposition to 350 W and the discharge time to 20 seconds, the output of the high frequency power source at the time of vapor deposition was set to 350 W, the discharge time was set to 30 seconds. A plastic container was produced in exactly the same manner as in Comparative Example 1.

[Experimental example]
The oxygen permeability of the plastic containers produced in Examples 1 to 7 and Comparative Examples 1 and 2 was measured.
The above-mentioned oxygen permeability is measured using a measuring instrument manufactured by MOCON, USA, under the conditions of a temperature of 23 ° C. and a humidity of 90% RH for a plastic container that has shrunk due to the internal stress remaining after molding [ Oxygen permeability was measured using the model name, OXTRAN.
In addition, about the plastic container, the circumference | surroundings of the opening part were coat | covered with the metal, and it measured in the state which provided the gas barrier property in the part without a gas barrier thin film.
The measurement results are shown in Table 1 below.

(Table 1)
┌─────┬───────────────────┬─────────┐ │ │ Oxygen permeability (cc / pkg ・ day) │ Barrier property improvement rate │ │ ├ ─────────┬─────────┤ (Undeposited / deposited) │ │ │ Undeposited sample │ Deposited sample │ │ ├───── ┼─────────┼─────────┼─────────┤ │Example 1 │ 0.054 │ 0.0030 │ 18 │ ├─── ──┼─────────┼─────────┼─────────┤ │Example 2 │ 0.055 │ 0.0030 │ 18 │ ├─ ────┼─────────┼─────────┼─────────┤ │Example 3 │ 0.056 │ 0.0030 │ 19 │ ├─────┼─────────┼─────────┼ ────────┤ │Example 4 │ 0.055 │ 0.0025 │ 22 │ ├─────┼─────────┼────────── │─────────┤ │Example 5 │ 0.056 │ 0.0025 │ 22 │ ├─────┼─────────┼──────── ──┼─────────┤ │Example 6 │ 0.055 │ 0.0055 │ 10 │ ├─────┼─────────┼────── ────┼─────────┤ │Example 7 │ 0.055 │ 0.0036 │ 15 │ ├─────┼─────────┼─── ──────┼─────────┤ │Comparative Example 1 │ 0.055 │ 0.0070 │ 8 │ ├─────┼─────────┼── ────────┼─────────┤ │Comparative Example 2 │ 0.054 │ 0 0063 │ 9 │ └─────┴─────────┴─────────┴─────────┘

  As apparent from Table 1 above, it was confirmed that the samples according to Examples 1 to 7 have a high gas barrier property due to significantly improved oxygen permeability.

  The present invention provides an uneven smooth surface by plasma treatment on the entire inner surface of a plastic molded container body such as a blow molded container body made of polyester resin, and further, silicon oxide or the like is provided through the uneven smooth surface by the plasma treatment. The present invention relates to a plastic container formed with a gas barrier thin film mainly composed of an inorganic oxide, and the plastic container is excellent in gas barrier properties for preventing permeation of oxygen gas, water vapor, carbon dioxide gas, etc. It is useful as a packaging container capable of filling and packaging contents such as goods and others.

It is a schematic block diagram which illustrates one example of the low temperature plasma chemical vapor deposition apparatus for manufacturing it about the plastic container which concerns on this invention. It is a schematic block diagram which illustrates one example of the low temperature plasma chemical vapor deposition apparatus for manufacturing it about the plastic container which concerns on this invention. It is a schematic block diagram which illustrates one example of the low temperature plasma chemical vapor deposition apparatus for manufacturing it about the plastic container which concerns on this invention. It is a schematic block diagram which illustrates one example of the low temperature plasma chemical vapor deposition apparatus for manufacturing it about the plastic container which concerns on this invention. It is a schematic block diagram which illustrates one example of the low temperature plasma chemical vapor deposition apparatus for manufacturing it about the plastic container which concerns on this invention. It is a schematic sectional view which illustrates one example of the layer composition about the plastic container concerning the present invention manufactured using the low temperature plasma chemical vapor deposition apparatus.

Explanation of symbols

B Plastic container 1 Plastic molded container body 2 Uneven surface by plasma treatment 3 Gas barrier thin film mainly composed of inorganic oxide

Claims (7)

A plastic molding characterized by providing an uneven smooth surface by plasma treatment on the entire inner surface of a plastic molded container body, and further laminating a gas barrier thin film mainly composed of an inorganic oxide on the entire surface including the uneven smooth surface. container. 2. The plastic container according to claim 1, wherein the plastic molded container body is a blow molded container body made of polyester resin. 2. The plastic container according to claim 1, wherein the plastic molded container body is a blow molded container body made of a polyolefin resin. 4. The plastic according to claim 1, wherein the uneven smooth surface has a center line average roughness Ra (μm) in a range of 0.01 <Ra <0.05. Made container. The plastic container according to any one of claims 1 to 4, wherein the gas barrier thin film mainly composed of an inorganic oxide is a silicon oxide vapor deposited thin film formed by a chemical vapor deposition method. The plastic container according to any one of claims 1 to 5, wherein the gas barrier thin film mainly composed of an inorganic oxide is a silicon oxide vapor deposited thin film formed by a low temperature plasma chemical vapor deposition method. Inline after molding the plastic molding container main body on the entire inner surface of the plastic molding container main body using a low-temperature plasma chemical vapor deposition apparatus with an uneven smooth surface by plasma treatment and a gas barrier thin film mainly composed of inorganic oxide. A method for producing a plastic container, characterized in that

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