JP5012762B2 - Manufacturing method for plastic containers - Google Patents

Description

  The present invention relates to a method for producing a plastic container having a gas barrier thin film on the inner surface of a plastic container main body using a high-frequency plasma CVD apparatus and having excellent gas barrier properties for preventing permeation of oxygen gas, water vapor and the like.

Conventionally, as one of packaging containers for filling and packaging various articles, there are various types of plastic containers molded by 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 used in various fields as an indispensable packaging container for filling and packaging various articles.

However, the above-mentioned plastic container has various disadvantages, but has several drawbacks.
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, as what improves the above problems in a plastic container, for example, the surface of the plastic container contains a gas barrier resin such as polyvinylidene chloride resin or ethylene-vinyl alcohol copolymer resin. A plastic plastic container having a gas barrier resin film formed by coating a gas barrier resin composition, or a plastic container formed by forming a silicon oxide thin film on the surface and / or inner surface of a plastic container main body by a plasma CVD method (See, for example, Patent Document 1, Patent Document 2, Patent Document 3, and the like).

  However, in the plastic container having the above gas barrier resin film, for example, in the case of a plastic container having a gas barrier resin film made of polyvinylidene chloride resin, permeation of oxygen gas, water vapor, carbon dioxide gas, etc. is prevented. The gas barrier properties are expected to have the desired effect, but when used as a packaging container and disposed of as garbage, for example, when disposed of by incineration, the gas barrier thin film contains chlorine atoms. Therefore, for example, chlorine atoms cause generation of toxic gases such as dioxins, etc., and there is a concern about the influence on human bodies, etc., so that plastic atoms having a gas barrier resin film made of this polyvinylidene chloride resin are used. Containers are not suitable for disposal and also cause problems such as environmental destruction and lack environmental suitability. It has a problem that.

  In the plastic container having the gas barrier resin film, for example, in the case of a plastic container having a gas barrier resin film made of an ethylene-vinyl alcohol copolymer, oxygen gas, Although the desired effect can be achieved with respect to the gas barrier property that prevents the permeation of carbon dioxide gas, etc., in the wet state, the gas barrier property that prevents the permeation of oxygen gas, water vapor, carbon dioxide gas, etc. significantly decreases, and is no longer necessary. A plastic container having a gas barrier resin film made of an ethylene-vinyl alcohol copolymer cannot withstand its use.

Further, in a plastic container formed by forming a silicon oxide thin film on the surface and / or inner surface of the plastic container body by the plasma CVD method, the plastic container body itself is, for example, at the time of molding or the contents of packaging. Since the silicon oxide thin film itself is inorganic and glassy, and further lacks flexibility, flexibility, etc. The silicon oxide thin film lacks the ability to follow changes such as expansion and contraction of the plastic container body, and cracks and the like are very easily generated in the silicon oxide thin film.
Thus, when a crack or the like occurs in the silicon oxide thin film, the gas barrier function is no longer lost, and the plastic oxide film is formed by forming the silicon oxide thin film on the surface and / or inner surface of the plastic container body by the plasma CVD method. The container cannot be used as a packaging container.

  Further, a plastic container formed by forming a silicon oxide thin film on the surface side of the plastic container main body by the plasma CVD method does not have a silicon oxide thin film on the inner surface side thereof, so that this plastic is still used. In plastic containers, plasticizers, stabilizers, other additives, residual monomers, etc. contained in the plastic composition are eluted, and these plasticizers, stabilizers, other additives, residual monomers, etc. are packaged. This may affect the quality of the product, change the quality of the product, modify the quality, and the plastic container may no longer be used.

  By the way, although a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the entire inner surface of the plastic container body, the gas barrier thin film is free of cracks and the like, and oxygen gas, water vapor, carbon dioxide gas. A high-frequency plasma CVD apparatus as shown in FIG. 6 has been proposed as an apparatus for providing a plastic having an extremely excellent gas barrier property that prevents the permeation of light and the like.

The high-frequency plasma CVD apparatus includes an external electrode 12 and an internal electrode 16. The external electrode is composed of a first external partial electrode 12a and a second external partial electrode 12b. The external partial electrodes 12a and 12b are combined, electrically connected to each other, and integrated with the external electrode 12. Is provided with a reaction chamber C having a slightly similar space that is slightly larger than the main portion of the plastic container main body 1 on which the thin film is to be applied (in the drawing, the main portion of the reaction chamber C and plastic The main part of the container body 1 is drawn in substantially the same shape).
The internal electrode 16 is disposed in the reaction chamber C. The internal electrode 16 is formed of a hollow body and includes a plurality of source gas blowing holes 16a. The internal electrode 16 includes a source gas supply pipe 17 made of a conductive material. Are connected. A vacuum source (not shown) is connected to the reaction chamber C via an exhaust pipe 15, and 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 grounded via the source gas supply pipe 17.

  In the above conventional apparatus, the discharge between the electrodes 12 and 16 due to the high-frequency current is utilized to generate plasma, and the vapor deposition layer is formed, and the vapor deposition layer is formed on the inner surface of the plastic container body 1 as shown in FIG. A plastic container A in which the thin film 2 made of is formed is obtained.

  However, in this high-frequency plasma CVD apparatus, the plasma cannot collide with the inner surface of the plastic container main body 1 with acceleration, so that a sufficient gas barrier thin film cannot be formed.

Japanese Utility Model Publication No. 5-35660 JP 2000-43875 A JP 2000-117881 A

  An object of the present invention is to use a high-frequency plasma CVD apparatus capable of forming a sufficiently thin gas barrier film by causing plasma to collide with the entire surface of the inner surface of a plastic container body with acceleration. To provide a method for producing a plastic container having a gas barrier thin film.

The invention according to claim 1 includes an external electrode and an internal electrode, and the external electrode includes a reaction chamber having a similar space slightly larger than the main part of the plastic container main body on which the thin film is to be deposited. The internal electrode is disposed in the reaction chamber, the internal electrode is formed of a hollow body, and includes a plurality of source gas blowing holes. The internal electrode is connected to a source gas supply pipe made of a conductive material, and the reaction chamber has a vacuum source. Is connected via an exhaust pipe, a high-frequency power source is connected to an external electrode via a matching unit, an internal electrode is grounded via a source gas supply pipe, and a plastic container body arranged in the external electrode is rotated. Using a high-frequency plasma CVD apparatus comprising means,
First, match both external partial electrodes so as to surround the plastic container body, electrically connect and integrate with the external electrodes,
Next, the reaction chamber is evacuated to a pressure capable of generating plasma by a vacuum pump through the source gas supply pipe, and the degree of vacuum is increased.
Next, an inert gas consisting of argon or helium is supplied through the source gas supply pipe and blown out from the source gas blowout hole while rotating the plastic container body by driving the prime mover and rotating the sprocket into the reaction chamber. At the same time, a high frequency voltage is applied between the external electrode and the internal electrode to generate a high frequency glow discharge in the reaction chamber,
Then, the inert gas ejected from the raw material gas blowout holes is converted into plasma, supplied uniformly throughout the reaction chamber, and collided with the inner surface of the rotating plastic container body with acceleration, A fine unevenness is formed on the inner surface of the plastic container body,
Next, again through the source gas supply pipe, the reaction chamber is evacuated to a pressure at which plasma can be generated by a vacuum pump, and the degree of vacuum in the reaction chamber is increased in the same manner as described above.
Next, the raw material gas is a raw material gas composition for vapor deposition prepared by using a monomer gas for vapor deposition composed of an organosilicon compound, oxygen gas, and inert gas through a raw material gas supply pipe in a plastic container body. It is ejected from the blowout hole into the reaction chamber,
Furthermore, a high-frequency voltage is applied between the external electrode and the internal electrode to generate a high-frequency glow discharge in the reaction chamber, and the high-frequency glow discharge causes the vapor deposition source gas composition supplied in the reaction chamber to be vapor-phased in the reaction chamber. React to produce a reaction product mainly composed of plasma silicon oxide,
Then, a gas barrier thin film made of a reaction product mainly composed of siliconized oxide is deposited on the inner surface of the plastic container body,
Thereafter, after a sufficient time to form the gas barrier thin film, the supply of the deposition source gas composition to the reaction chamber via the source gas supply pipe is stopped,
Next, the atmosphere is introduced into the reaction chamber,
Then, the gist of the method for producing a plastic container is to take out 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 container body.

  The gist of the invention of claim 2 is that the magnet is further provided around the external electrode in the high-frequency plasma CVD apparatus according to claim 1.

  Thus, according to the high-frequency plasma CVD apparatus of the first aspect of the present invention, the high-density plasma is further increased at a higher rate by the rotating means of the plastic container body disposed in the external electrode. It is possible to form a thin film that is made to collide with the inner surface, has a higher gas barrier property, and is firmly attached to the inner surface of the plastic container body.

  According to the high-frequency plasma CVD apparatus of the second aspect of the present invention, a high-density plasma is further generated by the rotating means of the plastic container body disposed in the external electrode while generating a magnetic field inside the reaction chamber. It is possible to form a thin film that collides with the inner surface of the plastic container body with high efficiency, has a higher gas barrier property, and is firmly attached to the inner surface of the plastic container body.

  Thus, the present invention solves the above-described problems related to plastic containers, and uses a high-frequency plasma CVD apparatus to dispose a plastic container body on which a thin film is to be deposited in an external electrode, and An internal electrode is placed inside, a high-frequency voltage is applied between the electrodes, and plasma is accelerated to collide with the inner surface of the plastic container body due to the lines of magnetic force and rotation of the internal electrode. The gist of the present invention is a method for producing a plastic container in which a gas barrier thin film is formed on the inner surface of a plastic container body by high-frequency glow discharge decomposition of a reactive gas.

  The plastic container manufactured by the method of the present invention has a reactive gas in the reaction chamber under reduced pressure by causing the plasma to collide with the inner surface of the plastic container body with a magnetic force, rotation of the plastic container body, etc. with acceleration. The high-frequency glow discharge decomposition has a gas barrier thin film firmly fixed to the inner surface of the plastic container body, has a high gas barrier property, and the thin film is firmly fixed to the inner surface of the plastic container main body and peels off. There is nothing.

As described above in detail, according to the plastic container manufacturing method using the high-frequency plasma CVD apparatus, it is possible to generate high-quality plasma with high density by generating a magnetic field inside the reaction chamber. Not only can the plasma collide with the inner surface of the plastic container body with acceleration, but it has a higher gas barrier property and forms a thin film that is firmly attached to the inner surface of the plastic container body. Is possible.
Furthermore, in the present invention, the high-density plasma collides with the inner surface of the plastic container body at a higher rate by the rotating means of the plastic container body, and has a higher gas barrier property. It is possible to form a thin film that is firmly attached.
In the present invention, a magnetic field is generated inside the reaction chamber, and the high-density plasma is collided with the inner surface of the plastic container main body with higher efficiency by the rotating means of the plastic container main body, thereby providing a higher gas barrier property. In addition, it is possible to form a thin film firmly attached to the inner surface of the plastic container body.
Thus, the plastic container manufactured according to the present invention uses a high-frequency plasma CVD apparatus, arranges the plastic container body on which the thin film is to be deposited in the external electrode, and arranges the internal electrode in the plastic container body. Then, a high frequency voltage is applied between the electrodes, and the plasma collides with the inner surface of the plastic container body with acceleration due to magnetic field lines, rotation of the plastic container body, etc., and the high frequency of the reactive gas in the reaction chamber under reduced pressure This is a plastic container in which a gas barrier thin film is formed by glow discharge decomposition. Plasma is accelerated and collides with the inner surface of the plastic container body by the rotation of the magnetic field lines and the plastic container body, and the reaction chamber is under reduced pressure. The gas burrs firmly adhered to the inner surface of the plastic container body by high-frequency glow discharge decomposition of the reactive gas Having sex film has high gas barrier properties, and a thin film is to have the advantage not to strongly fixed peeled to the inner surface of the plastic container body.

  FIG. 1 shows a high-frequency plasma CVD apparatus of the present invention.

The high frequency plasma CVD apparatus of the present invention 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 electrically connected to each other. And integrated with the external electrode 12.
The external electrode 12 includes a reaction chamber C having a slightly similar space that is slightly larger than the main portion of the plastic container body 1 on which a thin film is to be applied. The main part and the main part of the plastic container body 1 are drawn in substantially the same shape).

Further, 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 connected to a raw material gas supply pipe 17 made of a conductive material.
Further, a vacuum source (not shown) is connected to the reaction chamber C through an exhaust pipe 15.

  A high frequency power source 14 is connected to the external electrode 12 through a matching unit 13. On the other hand, the internal electrode 16 is grounded via the source gas supply pipe 17.

  Around the external electrode 12, a plurality of magnets 18 for generating a magnetic field in the reaction chamber C are disposed.

  The external electrode 12 described above is supported by the base 10 via the insulating plate 1.

  The source gas supply pipe 17 connected to the internal electrode 16 has an evaporation source material prepared by using an evaporation monomer gas such as an organosilicon compound, an oxygen gas, an inert gas, or the like, as indicated by an arrow P2. A gas composition gas is supplied.

Further, when the deposition source gas composition is supplied to the internal electrode 16 through the source gas supply pipe 17, the deposition source gas composition is blown out from the source gas blowing holes 16 a provided in the internal electrode 16.
It is desirable that a plurality of source gas blowing holes 16 a be provided in the internal electrode 16 in order to uniformly diffuse the blown deposition source gas composition into the reaction chamber C.

  Further, as shown by an arrow P1, the air in the reaction chamber C is exhausted by the vacuum source (vacuum pump) through the exhaust pipe 15.

  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, and plasma is generated on the inner surface of the plastic container body. A magnet that can be made to collide with acceleration, has a higher gas barrier property, and can form a thin film firmly attached to the inner surface of the plastic container body can be applied.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG. 1 will be described.

  First, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic container body 1, 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) or helium (He) is supplied into the plastic container main body 1 from the source gas supply pipe 17 and blown out from the source gas blowing hole 16. At the same time, the external electrode 12 and the internal electrode A high-frequency voltage is applied across 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.
The inert gas blown out from the raw material gas blowing hole 16 is converted into plasma in the reaction chamber C, and collides with the inner surface of the plastic container body 1 with acceleration, thereby forming fine irregularities on the inner surface of the plastic container body 1. Is done.
At that time, by generating a magnetic field by the magnet 18 in the reaction chamber C, it becomes possible not only to generate high-quality and high-quality inert gas plasma, but also to generate plasma on the inner surface of the plastic container body. It is possible to collide the inert gas with acceleration, and to efficiently form fine irregularities on the inner surface of the plastic 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 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. An object is generated, and this reaction product is applied to the entire inner surface of the plastic container body 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 generate plasma on the inner surface of the plastic container body. The reaction product is made to collide with acceleration, and a gas barrier thin film made of a reaction product mainly composed of an inorganic oxide such as silicon oxide formed into plasma is efficiently deposited on the inner surface of the plastic container body 1. It becomes possible.

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, the 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 container body 1 is taken out to produce the plastic container according to the present invention. it can.

In the above, the inside of the reaction chamber C is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to do.

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 1 × 10 ^-4 Torr level, preferably, it is desirable to adjust the degree of vacuum ^{1 × 10 -1 ~1 × 10 -2} Torr, also, as the time for forming a gas barrier thin film, 1 to 300 seconds position, preferably Is preferably adjusted to about 3 to 20 seconds.

In the above high-frequency plasma CVD apparatus, the formation of a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is performed by oxidizing the plasmaized source gas with oxygen gas over the entire inner surface of the plastic container body. It is formed as a thin film in the form of SiOX.
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 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 container body 1. There is an advantage that the adhesion between the gas barrier thin film mainly composed of inorganic oxide and the inner surface of the plastic container body 1 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. Since the degree of vacuum is lower than that of about 1 × 10 ⁻⁵ Torr, the vacuum state setting time at the time of replacement of the plastic container body 1 (predetermined after the plastic container body 1 is placed in the reaction chamber C) The time required to adjust the degree of vacuum) can be shortened.
Therefore, a stable degree of vacuum can be easily obtained, and the film forming process is stabilized.

In the present invention, an outer barrier thin film mainly composed of an inorganic oxide such as silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound is composed of a vapor deposition monomer gas such as an organosilicon compound and an oxygen gas. A chemical vapor reaction is performed, and the reaction product is deposited on the entire inner surface of the plastic container body 1 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 decrease toward 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 small at the interface with the inner surface of the plastic thin film container main body, the gas barrier thin film on the inner surface of the plastic container main body The adhesion becomes stronger.

  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 expansion rate of the plastic container body 1 immediately after filling the package contents in the plastic container body 1 is from 130%, and the shrinkage ratio of the surface area of the plastic container body 1 immediately after the molding of the plastic container body 1 is 3%. It consists of a gas barrier thin film mainly composed of silicon oxide that can follow 5% shrinkage and expansion.

  Thus, in the present invention, the gas barrier thin film mainly composed of silicon oxide is, for example, an X-ray electron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Sec-secondary Ion Mass Spectroscopy, SIMS). The above physical properties are confirmed by analyzing a gas barrier thin film mainly composed of silicon oxide using a method such as ion etching in the depth direction using a surface analyzer such as can do.

  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 100 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 less than 100 mm, and further 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 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.

  As described above, the plastic container according to the present invention manufactured using the high-frequency plasma CVD apparatus shown in FIG. 1 has a gas barrier thin film mainly composed of an inorganic oxide on the entire inner surface of the plastic container body 1. The configuration is provided.

  Next, as the plastic body 1 constituting the plastic container according to the present invention, for example, a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, a polyacrylic or polymethacrylic resin, a polyacrylic resin, a polystyrene resin Styrene-butadiene-acrylonitrile copolymer, polycarbonate resin, polyester resin or recycled polyester resin, polyamide resin, polyacetal resin, one or more of other resins are used as molding resin raw materials. For example, it is possible to use bottles, cups, cups, and other shapes of molded containers formed by molding the resin by, for example, extrusion molding, injection molding, blow molding, cast molding, thermoforming, and other molding methods. it can.

  Thus, as a plastic 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 polyolefin resin such as polyethylene resin or polypropylene resin.

In the above plastic container, a gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is deposited on the entire inner surface of the container.
Instead, a diamond-like carbon film may be formed on the entire inner surface of the container using, for example, a source gas composition containing acetylene as a source gas and argon as an inert gas.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG.

  Using polyethylene terephthalate resin 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 produce a 500-ml polyethylene terephthalate resin blow-molded bottle. Manufactured.

  Next, the polyethylene terephthalate resin blow-molded bottle produced above was mounted on the high-frequency plasma CVD apparatus shown in FIG. 1, and then the inside of the reaction chamber was lowered 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, and a magnetic field of 875 G is formed in the reaction chamber by a magnet disposed 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 inner surface of the blow-molded bottle was uneven and the moisture content on the inner surface of the blow-molded bottle was reduced.

  Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr by a vacuum pump, and 13.56 MHz is formed between the electrodes under a state in which a magnetic field of 875 G is formed in the reaction chamber by a magnet disposed around the external electrode. Then, a high frequency voltage of 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. .

  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 gas barrier thin film was formed to produce a plastic container according to the present invention.

After that, a plastic container shrunk under the influence of internal stress remaining after molding, was measured under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, manufactured by MOCON, USA [model name, OXTRAN] ] Was used to measure oxygen permeability.
As a result, the oxygen transmission rate was 0.025 cc / pg / atm / day, and it was found that the plastic container has a high gas barrier property.

  As in Example 1, except that a raw material gas composition composed of acetylene: oxygen gas: argon = 2: 3: 3 (slm) was supplied as a raw material composition while adjusting the gas flow rate to 35 ml / min. A plastic container according to the present invention was manufactured by forming a gas barrier thin film made of a diamond-like carbon deposited film having a thickness of 1200 mm on the inner surface of the plastic container.

After that, a plastic container shrunk under the influence of internal stress remaining after molding, was measured under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, manufactured by MOCON, USA [model name, OXTRAN] ] Was used to measure oxygen permeability.
As a result, the oxygen transmission rate was 0.021 cc / pg / atm / day, and it was found that the plastic container has a high gas barrier property.

Comparative Example 1
In the same manner as in Example 1, but without forming a magnetic field in the reaction chamber with a magnet, a gas barrier thin film made of a vapor deposition film mainly composed of silicon oxide having a thickness of about 1200 mm was formed on the inner surface of the blow molded bottle. Thus, a plastic container according to the present invention was manufactured.

After that, a plastic container shrunk under the influence of internal stress remaining after molding, was measured under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, manufactured by MOCON, USA [model name, OXTRAN] ] Was used to measure oxygen permeability.
As a result, it was found that the oxygen transmission rate was 0.047 cc / pg · atm · day, and the gas barrier property was inferior to the plastic containers of Examples 1 and 2.

Comparative Example 2
In the same manner as in Example 2, but without forming a magnetic field in the reaction chamber with a magnet, a gas barrier thin film made of a vapor-deposited diamond-like carbon film having a thickness of about 1200 mm was formed on the inner surface of the blow molded bottle, A plastic container according to the present invention was manufactured.

After that, a plastic container shrunk under the influence of internal stress remaining after molding, was measured under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, manufactured by MOCON, USA [model name, OXTRAN] ] Was used to measure oxygen permeability.
As a result, the oxygen permeability was 0.041 cc / pg / atm / day, and the gas barrier properties were found to be inferior to those of the plastic containers of Examples 1 and 2.

  Next, a high-frequency plasma CVD apparatus according to the present invention having a configuration different from that of the high-frequency plasma CVD apparatus shown in FIG.

The high frequency plasma CVD apparatus shown in FIG. 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 electrically connected to each other. The external electrode 12 is integrated with the external electrode 12, and the external electrode 12 is supported by a support device (not shown).
The external electrode 12 includes a reaction chamber C having a slightly similar space that is slightly larger than the main portion of the plastic container body 1 on which a thin film is to be applied. The main part and the main part of the plastic container body 1 are drawn in substantially the same shape).

Further, 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 source gas blowing holes 16a, and a source gas supply pipe 19 made of a conductive material is connected to the internal electrode 16.
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) by switching.

A high frequency power source 14 is connected to the external electrode 12 through a matching unit 13.
The internal electrode 16 is grounded via a source gas supply pipe 19.

Further, a source gas supply pipe 19 connected to the internal electrode 16 is formed in a mandrel shape, and a rotating means for 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 inner side of the O-ring mounting portion 22a is in contact with the outer end of the mouth of the plastic container main body 1, whereby the positional relationship with the plastic container main body 1 is maintained.

A bottle fixing jig 20 made of a metal body 20a and an insulator 20b is attached around the mouth of the plastic container body 1 so that the plastic container body 1 does not rotate.
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.

  As described above, the high-frequency plasma CVD apparatus shown in FIG. 2 is configured so that the internal electrode 16 is rotationally driven, and the internal electrode 16 rotates, so that the source gas can be supplied uniformly over the entire circumference. It is characterized in that the efficiency of vapor deposition is increased by causing the plasma to collide with the inner surface of the plastic container body 1 with acceleration.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG. 2 will be described.

  First, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic container body 1, 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 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.
The inert gas ejected from the rotating raw material gas blowing hole 16 is turned into plasma and supplied uniformly throughout the reaction chamber C, and the internal electrode 16 rotates, whereby the plastic container main body 1 is rotated. It is made to collide with an inner surface with acceleration, and fine unevenness is efficiently formed on the inner surface of the plastic container body 1.

  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 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. An object is generated, and this reaction product is allowed to collide with the inner surface of the plastic container body with acceleration and is deposited.
At that time, kinetic energy is imparted to the plasma by rotating the internal electrode 16, thereby improving the efficiency of reaction product generation, and the plasma collides with the inner surface of the plastic container body 1 with acceleration. Therefore, it is possible to efficiently 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 inner surface of the plastic container body 1.

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, the 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 container body 1 is taken out, leaving a partial region of the mouth of the blow molded bottle, The plastic container according to the invention can be manufactured.
In this container, there is a region that is not covered with the gas barrier thin film in a part of the mouth of the container body, but it is possible to configure a gas barrier packaging container by attaching a gas barrier cap to the mouth. it can.

  Other conditions, i.e., decompression in reaction chamber C, preparation of deposition source gas such as organosilicon compound, content of deposition monomer gas such as organosilicon compound in deposition source composition, inorganic such as silicon oxide Formation of gas barrier thin film mainly composed of oxide, gas barrier thin film mainly composed of inorganic oxide such as silicon oxide formed using vapor deposition monomer gas such as organic silicon compound, inorganic oxide such as silicon oxide As for the formation of a monomer gas for vapor deposition such as an organosilicon compound forming a gas barrier thin film as a main component, a plastic container body constituting a plastic container, and a diamond-like carbon film, the high-frequency plasma CVD of the present invention shown in FIG. As described in the description of the method of manufacturing the plastic container according to the present invention using the apparatus.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG.

  Using polyethylene terephthalate resin 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 produce a 500-ml polyethylene terephthalate resin blow-molded bottle. Manufactured.

  Next, the produced polyethylene terephthalate resin blow molded bottle was mounted on the high-frequency plasma CVD apparatus shown in FIG. 2, and then the inside of the reaction chamber was lowered to 0.06 Torr (8.0 Pa) by a vacuum pump.

  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 inner surface of the blow molded bottle was uniformly uneven, and the moisture content on the inner surface of the blow molded bottle was reduced.

  Next, the inside of the reaction chamber is again reduced to a vacuum degree of 0.06 Torr by a vacuum pump, a high frequency voltage is applied while rotating the internal electrode, and then hexamethyldisiloxane: oxygen gas: argon gas = 1: 3: A raw material gas composition consisting of 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 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.

Thereafter, the plastic container shrunk due to the influence of internal stress remaining after molding, the periphery of the mouth is covered with metal, and the gas barrier property is imparted to the portion without the gas barrier thin film, and the temperature is 23 ° C. and the humidity is 90 °. Under the condition of% RH, the oxygen transmission rate was measured using a measuring instrument [model name, OXTRAN] manufactured by MOCON, USA.
As a result, the oxygen transmission rate was 0.025 cc / pg / atm / day, and it was found that the plastic container has a high gas barrier property.

  Next, a high-frequency plasma CVD apparatus having a configuration different from that shown in FIG. 3 and the high-frequency plasma CVD apparatus shown in FIG. 2 will be described.

The high frequency plasma CVD apparatus shown in FIG. 3 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 electrically connected to each other. The external electrode 12 is integrated with the external electrode 12, and the external electrode 12 is supported by a support device (not shown).
The external electrode 12 includes a reaction chamber C having a slightly similar space that is slightly larger than the main portion of the plastic container body 1 on which a thin film is to be applied. The main part and the main part of the plastic container body 1 are drawn in substantially the same shape).

Further, 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 connected to 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.

A high frequency power source 14 is connected to the external electrode 12 through a matching unit 13.
The internal electrode 16 is grounded via the source gas supply pipe 17.

Further, the high-frequency plasma CVD apparatus is provided with a rotating means for the plastic container body 1.
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.
An 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 container body 1 is provided inside the O-ring attachment portion 28a.

The second ring is provided with a cylindrical portion 31 a that is fixed to the source gas supply pipe 17.
The cylindrical portion is provided with a slip ring 32 via a bearing 27.

  As described above, the high-frequency plasma CVD apparatus shown in FIG. 3 is configured such that the plastic container body 1 is rotationally driven, and since the plastic container body 1 rotates, the source gas is uniformly distributed over the entire circumference. It is characterized in that it can be supplied, and plasma is caused to collide with the inner surface of the plastic container body 1 with acceleration to increase the efficiency of vapor deposition.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG. 3 will be described.

  First, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic container body 1, 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), or the like is rotated into the reaction chamber C by driving the prime mover and rotating the sprocket 23 to rotate the plastic container body 1. 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.
The inert gas ejected from the rotating raw material gas blowing hole 16 is turned into plasma and supplied uniformly throughout the reaction chamber C, and the internal electrode 16 rotates, whereby the plastic container main body 1 is rotated. It is made to collide with an inner surface with acceleration, and fine unevenness is efficiently formed on the inner surface of the plastic container body 1.

  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 source 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 source gas supply pipe 17 in the plastic container body 1. The raw material gas blowing holes 16 are jetted into the reaction chamber C 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 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. An object is generated, and this reaction product is allowed to collide with the inner surface of the plastic container body with acceleration and is deposited.
At that time, kinetic energy is imparted to the plasma by the rotation of the plastic container body 1, thereby improving the efficiency of the generation of reaction products, and the plasma is accelerated on the inner surface of the plastic container body 1. It is possible to efficiently deposit a gas barrier thin film made of a reaction product mainly composed of an inorganic oxide such as silicon oxide that has been made to collide and is plasmatized into the inner surface of the plastic container body 1.

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, the plastic container according to the present invention can be manufactured by taking out the plastic container in which the gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the inner surface of the plastic container body.
In this container, there is a region that is not covered with the gas barrier thin film in a part of the mouth of the container body, but it is possible to configure a gas barrier packaging container by attaching a gas barrier cap to the mouth. it can.

  Other conditions, i.e., decompression in reaction chamber C, preparation of deposition source gas such as organosilicon compound, content of deposition monomer gas such as organosilicon compound in deposition source composition, inorganic such as silicon oxide Formation of gas barrier thin film mainly composed of oxide, gas barrier thin film mainly composed of inorganic oxide such as silicon oxide formed using vapor deposition monomer gas such as organic silicon compound, inorganic oxide such as silicon oxide As for the formation of a monomer gas for vapor deposition such as an organosilicon compound forming a gas barrier thin film as a main component, a plastic container body constituting a plastic container, and a diamond-like carbon film, the high-frequency plasma CVD of the present invention shown in FIG. As described in the description of the method of manufacturing the plastic container according to the present invention using the apparatus.

  Next, the method for producing the plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG.

  Using polyethylene terephthalate resin 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 produce a 500-ml polyethylene terephthalate resin blow-molded bottle. Manufactured.

  Next, the produced polyethylene terephthalate resin blow-molded bottle was mounted on the high-frequency plasma CVD apparatus shown in FIG. 3, and the reaction chamber was lowered to a vacuum degree of 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 into the reaction chamber, and a high frequency voltage of 13.56 MHz and 300 W is provided between the electrodes while rotating the blow molded bottle made of polyethylene terephthalate resin. Was applied to generate plasma, and this state was maintained for about 20 seconds.

  By performing this pretreatment, the inner surface of the blow molded bottle was uniformly uneven, and the moisture content on the inner surface of the blow molded bottle was reduced.

  Next, the inside of the reaction chamber is again reduced to a vacuum degree of 0.06 Torr by a vacuum pump, a high frequency voltage is applied while rotating the internal electrode, and then hexamethyldisiloxane: oxygen gas: argon gas = 1: 3: A raw material gas composition consisting of 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 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.

Thereafter, the plastic container shrunk due to the influence of internal stress remaining after molding, the periphery of the mouth is covered with metal, and the gas barrier property is imparted to the portion without the gas barrier thin film, and the temperature is 23 ° C. and the humidity is 90 °. Under the condition of% RH, the oxygen transmission rate was measured using a measuring instrument [model name, OXTRAN] manufactured by MOCON, USA.
As a result, the oxygen transmission rate was 0.025 cc / pg / atm / day, and it was found that the plastic container has a high gas barrier property.

  Next, the high frequency plasma CVD apparatus according to the present invention shown in FIG. 4 will be described.

  In this high-frequency plasma CVD apparatus, a magnet 18 is provided around the external electrode 12 of the high-frequency plasma CVD apparatus shown in FIG. 2, and the other configuration is the same as that of the high-frequency plasma CVD shown in FIG.

  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, and plasma is generated on the inner surface of the plastic container body. A magnet that can be made to collide with acceleration, has a higher gas barrier property, and can form a thin film firmly attached to the inner surface of the plastic container body can be applied.

Other configurations are the same as those of the high-frequency plasma CVD shown in FIG.

  As described above, the high-frequency plasma CVD apparatus shown in FIG. 4 can generate 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, the plastic container body 1 is configured to be rotationally driven, and since the plastic container body 1 rotates, the raw material gas can be supplied uniformly over the entire circumference, and It is characterized by increasing the efficiency of vapor deposition by causing the plasma to collide with the inner surface of the plastic container body 1 with acceleration.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG. 4 will be described.

  First, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic container body 1, 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 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. .
The inert gas ejected from the rotating raw material gas blowing hole 16 is turned into plasma and supplied uniformly throughout the reaction chamber C, and the internal electrode 16 rotates, whereby the plastic container main body 1 is rotated. It is made to collide with an inner surface with acceleration, and fine unevenness is efficiently formed on the inner surface of the plastic container body 1.
At that time, by generating a magnetic field by the magnet 18 in the reaction chamber C, it becomes possible not only to generate high-quality and high-quality inert gas plasma, but also to generate plasma on the inner surface of the plastic container body. It is possible to collide the inert gas with acceleration, and to efficiently form fine irregularities on the inner surface of the plastic container body 1.

  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 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. An object is generated, and this reaction product is allowed to collide with the inner surface of the plastic container body with acceleration and is deposited.
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 container body, and the plasma reaction product is collided with acceleration, and the inner surface of the plastic container body 1 is mainly made of an inorganic oxide such as silicon oxide that is converted into plasma efficiently. It is possible to deposit a gas barrier thin film made of the reaction product.

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, the plastic container according to the present invention can be manufactured by taking out the plastic container in which the gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the inner surface of the plastic container body.
In this container, there is a region that is not covered with the gas barrier thin film in a part of the mouth of the container body, but it is possible to configure a gas barrier packaging container by attaching a gas barrier cap to the mouth. it can.

  Other conditions, i.e., decompression in reaction chamber C, preparation of deposition source gas such as organosilicon compound, content of deposition monomer gas such as organosilicon compound in deposition source composition, inorganic such as silicon oxide Formation of gas barrier thin film mainly composed of oxide, gas barrier thin film mainly composed of inorganic oxide such as silicon oxide formed using vapor deposition monomer gas such as organic silicon compound, inorganic oxide such as silicon oxide As for the formation of a monomer gas for vapor deposition such as an organosilicon compound forming a gas barrier thin film as a main component, a plastic container body constituting a plastic container, and a diamond-like carbon film, the high-frequency plasma CVD of the present invention shown in FIG. As described in the description of the method of manufacturing the plastic container according to the present invention using the apparatus.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG.

  Using polyethylene terephthalate resin 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 produce a 500-ml polyethylene terephthalate resin blow-molded bottle. Manufactured.

  Next, the produced polyethylene terephthalate resin blow-molded bottle was mounted on the high-frequency plasma CVD apparatus shown in FIG. 4, and then the reaction chamber was lowered 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 300 W, and this state was maintained for about 20 seconds.

  By performing this pretreatment, the inner surface of the blow molded bottle was uniformly uneven, and the moisture content on the inner surface of the blow molded bottle was reduced.

  Next, the inside of the reaction chamber is again reduced to a vacuum degree of 0.06 Torr by a vacuum pump, a high frequency voltage is applied while rotating the internal electrode, and then hexamethyldisiloxane: oxygen gas: argon gas = 1: 3: A raw material gas composition consisting of 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 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.

Thereafter, the plastic container shrunk due to the influence of internal stress remaining after molding, the periphery of the mouth is covered with metal, and the gas barrier property is imparted to the portion without the gas barrier thin film, and the temperature is 23 ° C. and the humidity is 90 °. Under the condition of% RH, the oxygen transmission rate was measured using a measuring instrument [model name, OXTRAN] manufactured by MOCON, USA.
As a result, the oxygen transmission rate was 0.021 cc / pg / atm / day, and it was found that the plastic container has a high gas barrier property.

  Next, the high-frequency plasma CVD apparatus according to the present invention shown in FIG. 5 will be described.

  In this high-frequency plasma CVD apparatus, a magnet 18 is provided around the external electrode 12 of the high-frequency plasma CVD apparatus shown in FIG. 3, and the other configuration is the same as that of the high-frequency plasma CVD shown in FIG.

  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, and plasma is generated on the inner surface of the plastic container body. A magnet that can be made to collide with acceleration, has a higher gas barrier property, and can form a thin film firmly attached to the inner surface of the plastic container body can be applied.

  The other configuration is the same as that of the high-frequency plasma CVD shown in FIG.

  As described above, the high-frequency plasma CVD apparatus shown in FIG. 5 can generate 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, the plastic container body 1 is configured to be rotationally driven, and since the plastic container body 1 rotates, the raw material gas can be supplied uniformly over the entire circumference, and It is characterized by increasing the efficiency of vapor deposition by causing the plasma to collide with the inner surface of the plastic container body 1 with acceleration.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG. 5 will be described.

  First, both the external partial electrodes 12 a and 12 b are combined so as to surround the plastic container body 1, and are electrically connected and integrated with the external electrode 12.

  Next, the inside of the reaction chamber C is exhausted to a pressure at which plasma can be generated by a vacuum pump (not shown) through the exhaust pipe 15 to increase the degree of vacuum.

Next, an inert gas such as argon (Ar) or helium (He) is rotated into the reaction chamber C while the plastic container body 1 is rotated by driving the prime mover and rotating the sprocket 29. 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, and a magnetic field is generated in the reaction chamber C by the magnet 18. generate.
The inert gas ejected from the rotating raw material gas blowing hole 16 is converted into plasma and supplied into the reaction chamber C, and the plastic container body 1 is rotated to be applied to the inner surface of the plastic container body 1. It is made to collide uniformly in the circumferential direction, and fine irregularities are efficiently formed on the inner surface of the plastic container body 1.
At that time, by generating a magnetic field by the magnet 18 in the reaction chamber C, it becomes possible not only to generate high-quality and high-quality inert gas plasma, but also to generate plasma on the inner surface of the plastic container body. It is possible to collide the inert gas with acceleration, and to efficiently form fine irregularities on the inner surface of the plastic container body 1.

  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 source 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 source gas supply pipe 17 in the plastic container body 1. A reaction is carried out by applying a high-frequency voltage 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 while the material gas is blown into the reaction chamber C from an appropriate flow rate. A high-frequency glow discharge is generated in the 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 made to collide with the inner surface of the plastic container body 1 rotating with acceleration and deposited.
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 rotate the plastic container body 1. The kinetic energy is imparted to the plasma by the above, and the reaction product made into plasma collides with the inner surface of the plastic container main body with acceleration, and the inorganic oxide such as silicon oxide efficiently converted into plasma on the inner surface of the plastic container main body 1 It is possible to deposit a gas barrier thin film made of a reaction product mainly composed of.

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, the plastic container according to the present invention can be manufactured by taking out the plastic container in which the gas barrier thin film mainly composed of an inorganic oxide such as silicon oxide is formed on the inner surface of the plastic container body.
In this container, there is a region that is not covered with the gas barrier thin film in a part of the mouth of the container body, but it is possible to configure a gas barrier packaging container by attaching a gas barrier cap to the mouth. it can.

  Other conditions, i.e., decompression in reaction chamber C, preparation of deposition source gas such as organosilicon compound, content of deposition monomer gas such as organosilicon compound in deposition source composition, inorganic such as silicon oxide Formation of gas barrier thin film mainly composed of oxide, gas barrier thin film mainly composed of inorganic oxide such as silicon oxide formed using vapor deposition monomer gas such as organic silicon compound, inorganic oxide such as silicon oxide As for the formation of a monomer gas for vapor deposition such as an organosilicon compound forming a gas barrier thin film as a main component, a plastic container body constituting a plastic container, and a diamond-like carbon film, the high-frequency plasma CVD of the present invention shown in FIG. As described in the description of the method of manufacturing the plastic container according to the present invention using the apparatus.

  Next, a method for producing a plastic container according to the present invention using the high-frequency plasma CVD apparatus of the present invention shown in FIG.

  Using polyethylene terephthalate resin 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 produce a 500-ml polyethylene terephthalate resin blow-molded bottle. Manufactured.

  Next, the produced polyethylene terephthalate resin blow-molded bottle was mounted on the high-frequency plasma CVD apparatus shown in FIG. 5, and the inside of the reaction chamber was lowered 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 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 inner surface of the blow molded bottle was uniformly uneven, and the moisture content on the inner surface of the blow molded bottle was reduced.

  Next, the reaction chamber is again depressurized to a vacuum degree of 0.06 Torr by a vacuum pump, a high frequency voltage is applied while rotating a blow molded container made of polyethylene terephthalate resin, and then hexamethyldisiloxane: oxygen gas: argon gas = 1: 3: 3 (slm) of the raw material gas composition 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 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.

Thereafter, the plastic container shrunk due to the influence of internal stress remaining after molding, the periphery of the mouth is covered with metal, and the gas barrier property is imparted to the portion without the gas barrier thin film, and the temperature is 23 ° C. and the humidity is 90 °. Under the condition of% RH, the oxygen transmission rate was measured using a measuring instrument [model name, OXTRAN] manufactured by MOCON, USA.
As a result, the oxygen transmission rate was 0.021 cc / pg / atm / day, and it was found that the plastic container has a high gas barrier property.

As described above in detail, according to the present invention, it is possible not only to generate a high-density and high-quality plasma by generating a magnetic field inside the reaction chamber, but also to the inner surface of the plastic container body. It becomes possible to make the plasma collide with acceleration, and it is possible to form a thin film having a higher gas barrier property and firmly attached to the inner surface of the plastic container body.
Further, according to the present invention, the high-density plasma is caused to collide with the inner surface of the plastic container body at a higher rate by the rotation of the internal electrode or the rotation means of the plastic container body arranged in the external electrode. It is possible to form a thin film having gas barrier properties and firmly attached to the inner surface of the plastic container body.
Furthermore, according to the present invention, a magnetic field is generated inside the reaction chamber and the high-density plasma is made of plastic with higher efficiency by rotating the internal electrode or rotating the plastic container body disposed in the external electrode. It is possible to form a thin film that collides with the inner surface of the container body, has a higher gas barrier property, and is firmly attached to the inner surface of the plastic container body.
The plastic container manufactured by the method of the present invention uses a high-frequency plasma CVD apparatus, arranges a plastic container body on which a thin film is to be deposited in an external electrode, and arranges an internal electrode in the plastic container body. Then, a high-frequency voltage is applied between the electrodes, and the plasma collides with the inner surface of the plastic container body with a magnetic force line and / or rotation of the internal electrode or the plastic container body, and the reactivity in the reaction chamber is reduced under reduced pressure. This is a plastic container in which a gas barrier thin film is formed by high-frequency glow discharge decomposition of gas. Plasma is caused to collide with the inner surface of the plastic container body with acceleration due to the lines of magnetic force and / or rotation of the internal electrodes or the plastic container body. By high-frequency glow discharge decomposition of the reactive gas in the reaction chamber under reduced pressure. It has a gas barrier thin film that is firmly fixed to the inner surface of the stick container body, has a high gas barrier property, and has the advantage that the thin film is firmly fixed to the inner surface of the plastic container body and does not peel off. .
Therefore, the present invention is extremely useful as a packaging container for filling and packaging various articles.

It is a schematic sectional drawing of 1st Embodiment of the high frequency label CVD apparatus of this invention. It is a schematic sectional drawing of 2nd Embodiment of the high frequency label CVD apparatus of this invention. It is a schematic sectional drawing of 3rd Embodiment of the high frequency label CVD apparatus of this invention. It is a schematic sectional drawing of 4th Embodiment of the high frequency label CVD apparatus of this invention. It is a schematic sectional drawing of 1st Embodiment of the high frequency label CVD apparatus of this invention. It is a schematic sectional drawing of the conventional high frequency label CVD apparatus. It is sectional drawing of the plastic container using the conventional apparatus shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plastic container main body 2 Gas barrier thin film A Plastic container 10 Base 11 Insulation board 12a 1st external partial electrode 12b 2nd external partial electrode 12 External electrode 13 Matching device 14 High frequency power supply 15 Exhaust pipe 16 Internal electrode 16a Raw material gas blowing hole 17 Source gas supply pipe 18 Magnet C Reaction chamber 19 Source gas supply pipe 20a Metal body 20b Insulator 20b
20 Bottle fixing jig 21 O-ring 22a O-ring mounting portion 22 First ring 23 Sprocket 24 Chain 25 Second ring 26 Slip ring 27 Bearing 28a O-ring mounting portion 28 First ring 29 Sprocket 30 Chain 31 Second ring 31a Tubular part 32 Slip ring

Claims (2)

An external electrode and an internal electrode are provided, and the external electrode includes a reaction chamber having a slightly similar space that is slightly larger than the main part of the plastic container main body on which a thin film is to be deposited, and the internal electrode is disposed in the reaction chamber. The internal electrode is formed of a hollow body and includes a plurality of source gas blowing holes, a source gas supply pipe made of a conductive material is connected to the internal electrode, and a vacuum source is connected to the reaction chamber via an exhaust pipe. A high frequency power source is connected to the external electrode via a matching unit, the internal electrode is grounded via a source gas supply pipe, and a high frequency plasma CVD apparatus provided with a rotating means of a plastic container body disposed in the external electrode is used. And
First, match both external partial electrodes so as to surround the plastic container body, electrically connect and integrate with the external electrodes,
Next, the reaction chamber is evacuated to a pressure capable of generating plasma by a vacuum pump through the source gas supply pipe, and the degree of vacuum is increased.
Next, an inert gas consisting of argon or helium is supplied through the source gas supply pipe and blown out from the source gas blowout hole while rotating the plastic container body by driving the prime mover and rotating the sprocket into the reaction chamber. At the same time, a high frequency voltage is applied between the external electrode and the internal electrode to generate a high frequency glow discharge in the reaction chamber,
Then, the inert gas ejected from the raw material gas blowout holes is converted into plasma, supplied uniformly throughout the reaction chamber, and collided with the inner surface of the rotating plastic container body with acceleration, A fine unevenness is formed on the inner surface of the plastic container body,
Next, again through the source gas supply pipe, the reaction chamber is evacuated to a pressure at which plasma can be generated by a vacuum pump, and the degree of vacuum in the reaction chamber is increased as described above
Next, the organosilicon compound is driven into the rotating plastic container body through the source gas supply pipe while rotating the plastic container body by driving the prime mover and rotating the sprocket in the same manner as described above . A source gas composition for vapor deposition prepared using a monomer gas for vapor deposition, oxygen gas, and an inert gas, and jetted from a raw material gas blowing hole into a reaction chamber;
Furthermore, a high-frequency voltage is applied between the external electrode and the internal electrode to generate a high-frequency glow discharge in the reaction chamber, and the high-frequency glow discharge causes the vapor deposition source gas composition supplied in the reaction chamber to be vapor-phased in the reaction chamber. React to produce a reaction product mainly composed of plasma silicon oxide,
Then, a gas barrier thin film made of a reaction product mainly composed of siliconized oxide is deposited on the inner surface of the rotating plastic container body as described above ,
Thereafter, after a sufficient time to form the gas barrier thin film, the supply of the deposition source gas composition to the reaction chamber via the source gas supply pipe is stopped,
Next, the atmosphere is introduced into the reaction chamber,
Thereafter, a method for producing a plastic container, comprising taking out 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 container body. When a high frequency voltage is applied between the external electrode and the internal electrode to generate a high frequency glow discharge in the reaction chamber , a magnet is provided around the external electrode, and a magnetic field is generated inside the reaction chamber. The method for producing a plastic container according to claim 1.

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