JP6657766B2 - Plastic container and manufacturing method thereof - Google Patents

Description

  The present invention relates to a plastic container used for storing and transporting contents such as medicines, medical supplies, foods, and industrial parts.

  Glass containers are widely used as containers for storing and transporting contents. However, glass containers are easily broken and heavy. From the viewpoint of preventing cracking and reducing the weight, there is an increasing need for a plastic container having both gas barrier properties and transparency. The formation of a gas barrier film on the inner surface of a plastic container is generally performed by a plasma chemical vapor deposition (CVD) method (Patent Documents 1 and 2). However, it is technically difficult to perform the plasma-enhanced chemical vapor deposition method on a small container having an inner diameter of 40 mm or less used for a drink or a seasoning. In particular, in the case of a container having an elongated shape with an inner diameter of 20 mm or less and a length of 30 mm or more, when a gas barrier film is formed by a CVD method, plasma burning may occur locally. Due to plasma burning, the plastic container may be thermally deformed, a spark mark of abnormal discharge may be formed, or a local film thickness may be caused to make gas barrier property and transparency incompatible.

JP 2013-256708 A Patent No. 3746761

  Accordingly, an object of the present invention is to provide a plastic container in which a gas barrier film is entirely formed on a slender portion without a spark mark due to thermal deformation or abnormal discharge, and a method for manufacturing the same.

The first invention is
A plastic container having a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom closing the other end of the body, and having a gas barrier film on an inner surface, ,
The body has a portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less at one location,
The body has an inner diameter of 5 mm or more as a whole,
The opening is present at one end of the portion (A), or between the one end of the portion (A) and the opening, an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less; The opening exists at one end of the opening-side large diameter portion,
The other end of the portion (A) and the bottom portion are directly integrated, or a bottom portion having an inner diameter of more than 20 mm and a length of 200 mm or less is provided between the other end of the portion (A) and the bottom portion. The other end of the bottom-side large-diameter portion and the bottom portion having a diameter portion are directly integrated,
Said portion (A) 3 or the like by dividing the lengthwise, portion toward from the opening side to the bottom side _(A 1), part _(A 2), and partial _{(A 3),} said portion _{(A 1} ), The thickness of the gas barrier film at the center in the length direction is T ₁ , the thickness of the gas barrier film at the center of the portion (A ₂ ) in the length direction is T ₂ , and the bottom side of the portion (A ₃ ) in the case where the thickness of the gas barrier film on 3mm was T ₃ from the end,
T ₁ and T ₂ are not less than 10 nm and not more than 100 nm;
The ratio of T ₃ to the average thickness T _ave of T ₁ and T ₂ (T ₃ / T _ave ) is greater than 0.4;
This object is achieved by providing a plastic container.

“Hollow body extending substantially coaxially” means that the central axis of the hollow body is substantially straight. That is, the trunk is an elongated hollow portion. However, a part of the trunk may be reduced in diameter or increased in diameter. The trunk preferably has a circular cross section, but may have a shape other than a circle, such as an ellipse or a polygon. In this case, the “inner diameter” of the body refers to the maximum diameter of a circle included in the ellipse, polygon, or the like.
“Opening at one end of the body” means that the hollow shape is open at one end of the body without being closed.
The “bottom that blocks the other end of the body” is a portion that closes the other end of the body to form the bottom of the container. Although the shape of the bottom is not particularly limited, for example, when the cross-sectional shape of the body is circular, a hemisphere (the bottom is curved), a column (the bottom is flat), and a cone (the bottom is pointed) ). When the boundary between the torso and the bottom is clear (for example, when the torso is straight and the bottom is curved, or when the torso is straight and the bottom extends from the torso so as to bend from the torso) ) Determines the trunk and bottom based on the boundary. However, the length of the bottom (the height from the bottom of the inner surface of the container to the boundary with the body) is preferably within 20 mm. On the other hand, as shown in FIG. 1, when there is no boundary between the body and the bottom (the inner diameter gradually decreases from the opening to the bottom and the bottom is sharp, etc.), the bottom of the inner surface of the container (of the inner surface) The portion from the lowermost position (uppermost position) to 5 mm above is the bottom, and the portion above 5 mm is the trunk.
"Inner surface" refers to the inner wall of the plastic container.
“Having part (A) at one place” means that there is no part (A) other than the one part of the trunk. Here, the portion (A) may be reduced or expanded in the middle as long as the requirement for the inner diameter is satisfied.
"The other end of the portion (A) and the bottom portion are directly integrated" means that there is no other portion between the portion (A) and the bottom portion.
“The other end of the bottom-side large diameter portion and the bottom portion are directly integrated” means that there is no other portion between the bottom-side large diameter portion and the bottom portion.
The "partial central longitudinal section of (A _1)", in case of dividing two equal to the length portion (A _1), means the dividing line. Incidentally, in the division line, when the thickness of the gas barrier film is not constant, the average value of the thickness of the gas barrier film of the dividing line and T _1.
The "partial central longitudinal section of (A _2)", when partial divided two equal (A ₂₎ to the length direction means the dividing line. Incidentally, in the division line, when the thickness of the gas barrier film is not constant, the average value of the thickness of the gas barrier film of the dividing line and T _2.
When the thickness of the gas barrier film 3 mm above the bottom end of the portion (A ₃ ) is not constant, the average value of the “thickness T ₃ ” is defined as T ₃ .

  In the first aspect of the present invention, the gas barrier film is preferably a Si-containing film, a diamond-like carbon film, or an alumina film.

  In the first aspect of the present invention, a cap can be attached to the opening. Alternatively, a seal can be attached to the top surface of the opening.

The second invention provides
A vacuum chamber having an external electrode and an internal electrode accommodates a non-deposited plastic container inside the external electrode, and the distance between the tip of the internal electrode and the opening of the non-deposited plastic container is 0 mm or more and 30 mm or less. After the setting step, a gas barrier film is formed on the inner surface of the undeposited plastic container by plasma enhanced chemical vapor deposition.
With
The undeposited plastic container has a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom part closing the other end of the body,
The body has a portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less at one location,
The body has an inner diameter of 5 mm or more as a whole,
The opening is present at one end of the portion (A), or between the one end of the portion (A) and the opening, an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less; The opening exists at one end of the opening-side large diameter portion,
The other end of the portion (A) and the bottom portion are directly integrated, or a bottom portion having an inner diameter of more than 20 mm and a length of 200 mm or less is provided between the other end of the portion (A) and the bottom portion. The other end of the bottom-side large-diameter portion and the bottom portion having a diameter portion are directly integrated,
In the installation step, between the external electrode and the undeposited plastic container, along the outer shape of the undeposited plastic container, a dielectric on the opening side, a conductor on the bottom side, continuously disposed,
Around the said portion (A), from the open end of the moiety (A) of the dielectric down to the conductor length L _1, more than 50% of the length of the portion (A) 90 % or less, and the partial the conductor length L ₂ from the bottom end of the (a) up to the dielectric, and 10% to 50% the length of the portion (a),
An object of the present invention is to solve the above-mentioned problem by providing a method for manufacturing a plastic container.

  The “non-film-formed plastic container” means a plastic container on which the gas barrier film is not formed.

  ADVANTAGE OF THE INVENTION According to this invention, there is no spark mark of thermal deformation or abnormal discharge, and it can provide the plastic container by which the gas-barrier film | membrane is entirely formed in a slender part, and its manufacturing method. According to such a plastic container, the content fits into the elongated portion, and the content can be prevented from being damaged even when subjected to vibration. In addition, the overall gas barrier film can suppress oxidation, corrosion, decay, and alteration of the contents. In particular, since it can be fitted to the shape of the contents, the space volume in the container is small, the amount of gas (oxygen, water vapor) permeation is small, and the oxidation, corrosion, decay and deterioration of the contents are further suppressed. be able to.

It is a cross-sectional schematic diagram for demonstrating the trunk | drum and bottom in the plastic container in which the boundary of a trunk | drum and a bottom is unclear. FIG. 3 is a schematic cross-sectional view for explaining a shape of a plastic container. It is a cross-sectional schematic diagram for demonstrating the measurement location of the thickness of the gas barrier film in the part (A). FIG. 2 is a schematic cross-sectional view for explaining a dielectric and a conductor arranged around a portion (A) in plasma enhanced chemical vapor deposition. FIG. 3 is a diagram schematically illustrating an arrangement of a dielectric 11 and a conductor 12 according to the first embodiment.

1. Plastic container The present invention has a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom part closing the other end of the body, and a gas barrier film on the inner surface. A plastic container having
The body has a portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less at one location,
The body has an inner diameter of 5 mm or more as a whole,
The opening is present at one end of the portion (A), or between the one end of the portion (A) and the opening, an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less; The opening exists at one end of the opening-side large diameter portion,
The other end of the portion (A) and the bottom portion are directly integrated, or a bottom portion having an inner diameter of more than 20 mm and a length of 200 mm or less is provided between the other end of the portion (A) and the bottom portion. The other end of the bottom-side large-diameter portion and the bottom portion having a diameter portion are directly integrated,
Said portion (A) 3 or the like by dividing the lengthwise, portion toward from the opening side to the bottom side _(A 1), part _(A 2), and partial _{(A 3),} said portion _{(A 1} ), The thickness of the gas barrier film at the center in the length direction is T ₁ , the thickness of the gas barrier film at the center of the portion (A ₂ ) in the length direction is T ₂ , and the bottom side of the portion (A ₃ ) in the case where the thickness of the gas barrier film on 3mm was T ₃ from the end,
T ₁ and T ₂ are not less than 10 nm and not more than 100 nm;
The ratio of T ₃ to the average thickness T _ave of T ₁ and T ₂ (T ₃ / T _ave ) is more than 0.4.

1.1. Material of Body and Bottom In the present invention, as the material of the body and bottom constituting the plastic container, any of plastics used in conventional plastic containers can be adopted. For example, polyolefin, polyester, polyether, polyimide, acrylic resin, and the like. From the viewpoints of transparency, heat resistance, and strength, one or more selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, and polycarbonate are preferable.

1.2. Gas Barrier Film In the present invention, the composition of the gas barrier film formed on the inner surface of the plastic container is not particularly limited as long as it can suppress permeation of oxygen or water vapor. In particular, a SiO film, a SiON film, a SiOC film, a SiONC film, a Si-containing film such as a Si-containing diamond carbon film, a diamond-like carbon film (DLC film), or an alumina film is preferable. Among them, a DLC film is preferable because it is chemically inert and has flexibility to follow the expansion and contraction of the plastic container due to its flexibility. Note that the gas barrier film may be a stack of a plurality of films having different compositions.

  Examples of the DLC film include an amorphous carbon film, a hydrogenated amorphous carbon film, a tetrahedral amorphous carbon film, and a hydrogenated tetrahedral amorphous carbon film. The DLC film may contain nitrogen or oxygen. In that case, the number of nitrogen atoms and the number of oxygen atoms are preferably 20 or less, more preferably 15 or less, respectively, for 100 carbon atoms. Each number of atoms can be analyzed by ESCA.

  The thickness of the gas barrier film may satisfy predetermined requirements in the portion (A) described later. The lower limit of the thickness of the gas barrier film in the portion other than the portion (A) is preferably 10 nm or more, more preferably 15 nm or more, and the upper limit is preferably 120 nm or less, more preferably 100 nm or less.

1.3. Shape of Plastic Container As described above, the plastic container has a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom part closing the other end of the body. I have.

1.3.1. Body The body is a hollow portion that extends substantially coaxially. The body has an inner diameter of 5 mm or more as a whole. That is, it does not have a portion having an inner diameter smaller than the portion (A) described later.

  The sectional shape of the body is not particularly limited, but is preferably circular. This is because it becomes easier to form the gas barrier film uniformly and uniformly. However, a shape other than a circular shape such as an ellipse or a polygonal shape is also possible. The “inner diameter” in this case refers to the maximum diameter of a circle that can be included in the polygon or the like.

(Part (A))
In the present invention, the body has a portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less at one location. The trunk may have a large-diameter portion on the opening side or a large-diameter portion on the bottom side in addition to the portion (A).

It is preferable that the inner diameter of the portion (A) is smaller in that the effect of the present invention becomes more remarkable. That is, the upper limit of the inner diameter of the portion (A) is preferably 18 mm or less, more preferably 15 mm or less. In addition, it is preferable that the length of the portion (A) is long from the viewpoint that the effect of the present invention becomes more remarkable. That is, the lower limit of the length of the portion (A) is preferably at least 40 mm, more preferably at least 50 mm.
The lower limit of the inner diameter of the portion (A) is preferably 7 mm or more, more preferably 10 mm or more. The upper limit of the length of the portion (A) is preferably 120 mm or less, more preferably 100 mm or less.

(Open side large diameter part, bottom side large diameter part)
In the present invention, the trunk may have an opening-side large-diameter portion and a bottom-side large-diameter portion other than the portion (A). The large diameter portion on the opening side means a portion having an inner diameter of more than 20 mm and a length of 100 mm or less. Further, the bottom-side large diameter portion refers to a portion having an inner diameter of more than 20 mm and a length of 200 mm or less. Needless to say, when the inner diameter is large (more than 20 mm) such as the large diameter portion on the opening side or the large diameter portion on the bottom side, the gas barrier film can be easily and uniformly formed. Therefore, the upper limit of the inner diameter of these large diameter portions is not particularly limited.

1.3.2. Opening The plastic container according to the present invention has an opening at one end of the body. The hollow shape is open at one end of the body without being closed. The contents such as pharmaceuticals can be introduced into the container from the opening.

1.3.3. Bottom In the plastic container according to the present invention, a bottom is provided at the other end of the body, and the other end of the body is closed by the bottom. That is, the bottom closes the other end of the body to form the bottom of the container. For example, when the cross-sectional shape of the body is circular, the shape of the bottom may be hemispherical, cylindrical, conical, or the like. When the boundary between the torso and the bottom is clear (for example, when the torso is straight and the bottom is curved, or when the torso is straight and the bottom extends from the torso so as to bend from the torso) ) Determines the trunk and bottom based on the boundary. However, the length of the bottom (the height from the bottom of the inner surface of the container to the boundary with the body) is preferably within 20 mm. On the other hand, as shown in FIG. 1, when there is no boundary between the body and the bottom (the inner diameter gradually decreases from the opening to the bottom and the bottom is sharp, etc.), the bottom of the inner surface of the container (of the inner surface) The portion from the lowermost position (uppermost position) to 5 mm above is the bottom, and the portion above 5 mm is the trunk.

1.3.4. The positional relationship between the trunk, the opening, and the bottom will be described with reference to FIG. Hereinafter, the description will be made with the opening side of the container as the “one end” side and the bottom side of the container as the “other end” side. FIG. 2 shows an example in which the inner diameter of the portion (A) is the upper limit value of 20 mm. FIG. 2 illustrates a mode in which the inner surface shape of the portion (A) is linear in the length direction, but the present invention is not limited to this mode. The inner surface shape of the portion (A) may be curved in the length direction, or may be constituted by a plurality of straight lines. Further, FIG. 2 illustrates an embodiment in which the inner surface shape of the opening-side large-diameter portion and the bottom-side large-diameter portion described later is configured by two straight lines, but the present invention is not limited to this embodiment. The inner surface shape of the opening-side large-diameter portion or the bottom-side large-diameter portion may be linear in the length direction, may be curved, or may be configured by three or more straight lines.

  In the present invention, the trunk including the portion (A), the opening, and the bottom adopt any one of the four configurations described below. By adopting this configuration, it is obvious that the trunk does not have “a part having an inner diameter of 5 mm or more and 20 mm or less and less than 30 mm in length” or “a part having an inner diameter of 5 mm or more and 20 mm or less and more than 150 mm in length”.

  The shape of the plastic container according to the present invention can be a shape as shown in FIG. That is, the trunk 2 is composed of the portion (A). Specifically, the opening 1 is present at one end of the portion (A), and the other end of the portion (A) and the bottom 3 are directly integrated.

  Alternatively, the shape of the plastic container according to the present invention can be a shape as shown in FIG. That is, the upper part of the body part 2 can have a large diameter and the lower part can have a small diameter. Specifically, an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less is provided between one end of the portion (A) and the opening 1, and the opening 1 exists at one end of the opening-side large-diameter portion. In addition, the other end of the portion (A) and the bottom 3 are directly integrated.

  Alternatively, the shape of the plastic container according to the present invention can be a shape as shown in FIG. That is, the upper part of the body part 2 can have a small diameter and the lower part can have a large diameter. Specifically, an opening 1 is present at one end of the portion (A), and a bottom-side large-diameter portion having an inner diameter of more than 20 mm and a length of 200 mm or less between the other end of the portion (A) and the bottom. And the other end of the large diameter portion on the bottom side and the bottom portion are directly integrated.

  Alternatively, the shape of the plastic container according to the present invention can be a shape as shown in FIG. That is, the upper portion of the body 2 can have a large diameter, the middle portion can have a small diameter, and the lower portion can have a large diameter. Specifically, between the one end of the portion (A) and the opening 1, there is an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less, and an opening exists at one end of the opening-side large-diameter portion. And a bottom-side large-diameter portion having an inner diameter of more than 20 mm and a length of 200 mm or less between the other end of the portion (A) and the bottom portion, and the other end of the bottom-side large-diameter portion is directly integrated with the bottom portion. It has been.

1.3.5. Container thickness (wall thickness)
The thickness (wall thickness) of the body and bottom of the plastic container according to the present invention is not particularly limited, but the lower limit is preferably 0.2 mm or more, more preferably 0.3 mm or more, and the upper limit is preferably. Is 1.5 mm or less, more preferably 1.0 mm or less. With such a thickness, a plastic container having sufficient strength and low cost can be obtained. Further, plasma chemical vapor deposition described below can be performed more appropriately.

1.3.6. Volume The plastic container according to the present invention has a lower limit of the volume of preferably 5 cm ³ or more, more preferably 10 cm ³ or more, further preferably 15 cm ³ or more, and the upper limit is preferably 500 cm ³ or less, more preferably 100 cm ³ or less. It is. The present invention is characterized in that a gas barrier film is uniformly and uniformly formed on the inner surface of such a small container.

1.4. Thickness condition of gas barrier film in part (A) As shown in FIG. 3, the plastic container according to the present invention divides the part (A) into three equal parts in the length direction, and the part is divided from the opening side to the bottom side. (A ₁ ), portion (A ₂ ), portion (A ₃ ), the thickness of the gas barrier film at the central portion in the length direction of the portion (A ₁ ) is T ₁ , and the central portion in the length direction of the portion (A ₂ ). In the case where the thickness of the gas barrier film is T ₂ and the thickness of the gas barrier film 3 mm above the bottom end of the portion (A ₃ ) is T ₃ , the following thickness conditions are satisfied.

First, in the portion (A) of the plastic container according to the present invention, T ₁ and T ₂ are 10 nm or more and 100 nm or less. Thereby, sufficient gas barrier properties can be secured in the portion (A). The lower limits of T ₁ and T ₂ are preferably 25 nm or more, and the upper limits are preferably 75 nm or less.

In the portion (A) of the plastic container according to the present invention, the ratio of T ₃ to the average thickness T _ave of T ₁ and T ₂ (T ₃ / T _ave ) is more than 0.4. That is, it can be said that in the portion (A), the gas barrier film is formed uniformly and uniformly. The lower limit of T ₃ / T _ave is preferably 0.6 or more, more preferably 0.62 or more, and still more preferably 0.65 or more, and the upper limit is preferably 0.9 or less, more preferably 0.8 or less, More preferably, it is 0.78 or less.

1.5. Gas Barrier Property The plastic container according to the present invention preferably has an oxygen permeability (per container) at 23 ° C. and 50 RH% of less than 0.0030 cc / pkg / 24 h · air, more preferably less than 0.0020 cc / pkg / 24 h · air. , 0.0010 cc / pkg / 24 h · air.
The oxygen permeability at 23 ° C. 50 RH% per unit area is preferably less than ^{0.96cc / m 2 / 24h · air} , more preferably less than ^{0.64cc / m 2 / 24h · air} , 0.48cc / m ^It is more preferably less than ² / 24h · air.
On the other hand, in the plastic container according to the present invention, the water vapor transmission rate (per container) at 40 ° C. and 90 RH% is preferably less than 0.0050 g / pkg / 24 h, more preferably less than 0.0035 g / pkg / 24 h.
Further, water vapor permeability at 40 ° C. 90 RH% per unit area is preferably less than 1.6g ^/ m 2 ^/ 24h, less than 1.1g ^/ m 2 ^/ 24h, more preferred.

1.6. Sealing of Container The plastic container according to the present invention can be sealed by attaching a cap to the opening. Alternatively, sealing can be performed by attaching a seal to the top surface of the opening. The cap can take various forms, such as a screw type, a plug type, and a fitting type. For the seal, a gas barrier film in which a film having an aluminum foil or a gas barrier film is laminated with another film may be used, and this may be attached by heat sealing or using an adhesive or an adhesive. The plastic container according to the present invention can improve the gas barrier properties of the entire container by performing vacuuming, filling an inert gas, or the like in accordance with the properties of the contents. Thereby, the deterioration of the contents can be further suppressed.

  As described above, the plastic container according to the present invention has the gas barrier film formed entirely on the elongated portion (A). According to such a plastic container, the content fits into the elongated portion, and the content can be prevented from being damaged even when subjected to vibration. Further, oxidation, corrosion, decay, and alteration of the contents can be suppressed by the gas barrier film formed entirely. In particular, since it can be fitted to the shape of the contents, the space volume in the container is small, the amount of gas (oxygen, water vapor) permeation is small, and the oxidation, corrosion, decay and deterioration of the contents are further suppressed. be able to.

2. Plastic Container Manufacturing Method The plastic container according to the present invention can be manufactured by the following manufacturing method. That is, the production method according to the present invention
A vacuum chamber having an external electrode and an internal electrode accommodates a non-deposited plastic container inside the external electrode, and the distance between the tip of the internal electrode and the opening of the non-deposited plastic container is 0 mm or more and 30 mm or less. After the setting step, a gas barrier film is formed on the inner surface of the undeposited plastic container by plasma enhanced chemical vapor deposition.
With
The undeposited plastic container has a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom part closing the other end of the body,
The body has only one portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less,
The body has an inner diameter of 5 mm or more as a whole,
The portion (A) constitutes the opening, or the portion (A) has an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less between the portion (A) and the opening, and A diameter portion constitutes the opening,
The portion (A) and the bottom are directly integrated with each other, or the portion (A) has a bottom-side large-diameter portion having an inner diameter of more than 20 mm and a length of 200 mm or less between the portion (A) and the bottom. The bottom side large diameter portion and the bottom portion are directly integrated,
In the installation step, between the external electrode and the undeposited plastic container, along the outer shape of the undeposited plastic container, a dielectric on the opening side, a conductor on the bottom side, continuously disposed,
Around the said portion (A), from the open end of the moiety (A) of the dielectric down to the conductor length L _1, more than 50% of the length of the portion (A) 90 % or less, and the partial the conductor length L ₂ from the bottom end of the (a) up to the dielectric, and 10% to 50% the length of the portion (a),
It is characterized by the following.

2.1. Installation process 2.1.1. Undeposited plastic container An undeposited plastic container (a plastic container having no gas barrier film) satisfies the above-described requirements for the body, opening, and bottom. That is, the undeposited plastic container has a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom that closes the other end of the body. It has only one portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less, and the body has an inner diameter of 5 mm or more as a whole, and the portion (A) forms an opening; Alternatively, there is an opening-side large-diameter portion having an inner diameter of more than 20 mm and a length of 100 mm or less between the portion (A) and the opening, and the opening-side large-diameter portion forms an opening. Are directly integrated with each other, or have a bottom-side large-diameter portion having an inner diameter of more than 20 mm and a length of 200 mm or less between the portion (A) and the bottom portion, and the bottom-side large-diameter portion and the bottom portion are directly connected to each other. It is one. Such a non-film-formed plastic container is formed, for example, by molding a test tube-shaped preform by known injection molding, extrusion molding, or the like, and then using a mold, by biaxial stretch blow molding, direct blow molding, or the like. It can be easily obtained by molding into.

2.1.2. Vacuum chamber with external and internal electrodes Vacuum chambers with external and internal electrodes are known per se. For example, a vacuum chamber having an external electrode and an internal electrode as described in JP-A-2013-256708 can be employed. The vacuum chamber is usually connected to exhaust means (exhaust pumps, valves, etc.), gas supply means (raw materials, mass flow controllers, valves, etc.), power supply means (power supplies, matching devices, valves, etc.) and the like.

  In the present invention, an undeposited plastic container having a predetermined shape is accommodated inside the external electrode. The inner wall of the external electrode has a shape corresponding to the shape of the container. External electrodes divided in the circumferential direction or the vertical direction may be used in an airtight combination with each other. The material of the external electrode is not particularly limited, and may be the same as a known external electrode. The external electrode is connected via a matching device to a power supply (high-frequency power supply, low-frequency power supply, AC power supply, microwave power supply, or the like) capable of generating an AC electric field for generating plasma discharge.

  The internal electrode is connected to a ground potential and located outside the opening of the container. Various materials such as tungsten, stainless steel, and aluminum can be adopted as the material of the internal electrode. It is also possible to introduce gas through the inside of the internal electrode. For example, a single or a plurality of pores are provided at the tip of the hollow cylindrical internal electrode so that gas can be led out. In this case, when the internal electrode is inserted into the container and the film formation is repeated, foreign matter adheres to the internal electrode, and discharge failure is likely to occur. Further, since the container targeted by the present invention has a small inner diameter, the internal electrode is not inserted into the container from the viewpoint of avoiding contact between the internal electrode and the inner wall of the container. In the installation step according to the present invention, the internal electrode is installed above the opening of the container without being inserted into the container. Specifically, the distance between the opening and the inner front end is 0 mm or more and 30 mm or less.

2.1.3. Dielectric and Conductor In the installation step according to the present invention, as shown in FIG. 4 (A), between the external electrode 15 and the undeposited plastic container 20, along the outer shape of the undeposited plastic container 20, the opening side , And the conductor 12 is continuously arranged on the bottom side.

As the material of the dielectric 11, a material which can suppress the concentration of plasma, has high heat resistance, high pressure resistance, high strength, and has a small high-frequency loss is selected. For example, glass, ceramic, plastic, and the like. In particular, plastic has the advantages of not cracking, light weight, and easy moldability, and is most suitable as a dielectric by using a composition having heat resistance. For example, at least one selected from a hard vinyl chloride resin, a fluorine resin, a polycarbonate resin, and a polyetheretherketone resin is preferable. In addition, from the viewpoint of dielectric properties and insulating properties, the thickness of the dielectric (the thickness in the direction orthogonal to L ₁ and L ₂ ) is preferably 1 mm or more and 20 mm or less. More preferably, it is 5 mm or more and 15 mm or less.

  The material of the conductor 12 may be a material having conductivity enough to induce plasma. For example, stainless steel, aluminum and the like. Aluminum is preferred in terms of conductivity and lightness.

  Conventionally, plasma is formed in a form in which the outer periphery of a container is covered only with an external electrode (Japanese Patent No. 3747661), or in a form in which only a dielectric is arranged between the external electrode and the container (Japanese Patent Application Laid-Open No. 2013-256708). Chemical vapor deposition was being performed. However, in such a form, the present inventor has found that plasma does not spread to the bottom of the portion (A) in a container having a portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less. It was found that the plasma density increased locally. As a result, there is a problem that plasma burning occurs on the opening side and the central portion of the portion (A), and the film becomes locally thick, resulting in poor appearance.

  Therefore, in the present invention, the dielectric 11 and the conductor 12 are vertically combined between the external electrode 15 and the container 20. As shown in FIG. 4, the same dielectric 11 or conductor 12 is arranged in the circumferential direction. Alternatively, the cylindrical dielectric 11 and the conductor 12 are vertically combined. It is preferable that the external electrode 15 and the individual dielectrics 11 and conductors 12 are arranged in an airtight manner. Thereby, abnormal discharge can be suppressed. On the other hand, the inner surfaces of the dielectric 11 and the conductor 12 have a shape corresponding to the shape of the container 20. There may be a gap between the container 20 and the dielectric 11 and the conductor 12.

  In the present invention, by arranging the conductor 12 on the bottom side of the portion (A), plasma can be induced to the bottom side. On the other hand, by disposing the dielectric 11 on the opening side of the portion (A), it is possible to prevent the plasma from concentrating on the opening side and the central portion. Therefore, plasma burning on the opening side and the central portion of the portion (A) can be suppressed, and thickness unevenness of the gas barrier film can be suppressed on the entire inner surface of the portion (A).

More specifically, according to the present invention, as shown in FIG. 4B, the length of the dielectric 11 from the opening side end of the portion (A) to the conductor 12 around the portion (A). the L _1, and 90% or less than 50% of the length of the portion (a), the portion from the bottom end of the conductor 12 up to the dielectric 11 of (a) a length _{L 2,} part (a ) Is 10% or more and 50% or less of the length.
The length L _1, the lower limit is preferably part (A) of more than 75% of the length, the upper limit is preferably not more than 88%.
The length L _2, the lower limit is preferably part (A) 12% or more the length of the upper limit is preferably 25% or less.
If L ₁ is too short, there is a possibility not prevent plasma concentration of the open side and the central portion. On the other hand, if L2 is too short, the plasma attraction effect will be insufficient. By setting L ₁ and L ₂ within the above range, the gas barrier film can be formed on the entire inner surface of the portion (A) by only slightly adjusting the matching point without making the power supply severely matched.

2.2. Film forming step In the present invention, in the above-described setting step, the undeposited plastic container is housed inside the external electrode and inside the dielectric and the conductor, and the internal electrode is placed at a predetermined position outside the container opening. After installation at the location, a gas barrier film can be formed in the container by plasma enhanced chemical vapor deposition. The plasma chemical vapor deposition method is a method in which a raw material gas is dissociated and ionized by plasma generated under reduced pressure to generate a film-forming species, and is deposited and deposited on an adherend.

  Examples of the source gas for the Si-containing film include silane, tetraethoxysilane, trimethylsiloxane, hexamethyldisiloxane, hexamethyldisilazane, and the like. The reaction gas is oxygen, nitrogen, ammonia or the like.

  Examples of the raw material gas for the DLC film include unsaturated hydrocarbon compounds such as acetylene, ethylene, and propylene; saturated hydrocarbon compounds such as methane, ethane, propane, and cyclohexane; and aromatic hydrocarbon compounds such as benzene, toluene, and xylene. . These may be used alone or in combination of two or more. Among them, it is preferable to use ethylene or acetylene gas alone.

  The raw material gas for the Si-containing DLC film may be a Si-containing hydrocarbon gas or a mixture of the raw material gas for the DLC film and an organosilicon compound.

  As a raw material gas for the alumina film, trimethylaluminum or the like is used. Oxygen is used as a reaction gas.

  A small amount of hydrogen or an organic compound may be mixed in the above-mentioned source gas. Further, the source gas may be diluted with a rare gas such as argon or helium.

  When a gas barrier film is formed by a plasma chemical vapor deposition method, vacuum evacuation (decompression) and gas introduction are performed, and when the internal pressure reaches a predetermined pressure (degree of vacuum), the source gas is turned into plasma to form a film. The internal pressure at the time of film formation is preferably 1 Pa or more and 50 Pa or less in consideration of good film quality and physical properties and the time required for film formation. The source gas may be introduced through the internal electrode or directly into the chamber. In particular, by using the gas inlet tube and the internal electrode together, the number of components can be reduced, and it is possible to prevent the film-forming components from adhering to the components, dropping, and entering foreign matter into the container film formation.

  The inside of the chamber is set to a predetermined degree of vacuum, a raw material gas is supplied, and a voltage is applied between the external electrode and the internal electrode at the ground potential to generate plasma inside the container housed in the external electrode. Thus, a gas barrier film can be formed on the inner surface of the container. For example, when a high-frequency power supply is used as the power supply, the frequency can be 13.56 MHz for general use. The output is 50-1000W, preferably 100-500W. The film forming time can be set to 0.2 to 4.0 seconds, preferably 1.0 to 3.0 seconds.

  As described above, according to the manufacturing method of the present invention, by arranging the dielectric and the conductor in combination under the predetermined condition between the external electrode and the container, the power supply is not severely matched. In both cases, the gas barrier film can be formed on the entire inner surface of the portion (A) of the container only by slightly adjusting the matching point.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples and Comparative Examples.

1. Examples 1-3, Comparative Examples 1-4
1.1. Gas Barrier Film Forming Method and Film Forming Conditions A gas barrier film was formed on the inner surface of the plastic container having the portion (A) by a plasma chemical vapor deposition apparatus as shown in FIG. 4, and various evaluations were made. Specifically, in a film forming apparatus having a space volume of 350 cm ³ , the container is installed, the chamber is evacuated, the ultimate pressure inside the container is set to 15 Pa, and a source gas is introduced to form a film for 3.0 seconds. Was done. High-purity acetylene was used as a source gas, and the gas flow rate was 100 sccm. A 13.56 MHz high frequency power supply was used as a plasma generation power supply, and the set output was set to 250 W. As the internal electrode, an electrode having a diameter of 10 mm and a pore of 1 mm serving also as a gas introduction tube was used. The position of the pore was at the tip of the tube, and the number of pores was one. The conductor and the dielectric were respectively disposed between the external electrode and the container. Aluminum (15 mm thick) was used as the conductor, and fluororesin (15 mm thick) was used as the dielectric. The portion (A) of the container is divided into four equal parts in the length direction, and positions a, b, c, and d are set from the opening side to the bottom side. As shown in Table 1 below, the arrangement of the dielectric and the conductor is determined. It was changed. In “Arrangement 5” in Table 1 below, the d position was further divided into two equal parts in the vertical direction, and the upper side was the d-1 position, and the lower side was the d-2 intention. For reference, FIG. 5 schematically shows the arrangement of the dielectric 11 and the conductor 12 in the first embodiment.

1.2. Container A container having a portion (A) was produced by injection blow molding polyethylene terephthalate. As shown in FIG. 2 (A), the entire body of the manufactured container had a portion (A) (wall thickness 0.5 mm, inner diameter 20 mm, length 50 mm). The bottom was hemispherical.

1.3. Evaluation 1.3.1. Appearance The presence of plasma burns and abnormal discharge traces and uneven color were visually observed. The evaluation criteria were as follows. Table 1 shows the results.
A: Overall brown
It is presumed that the film is formed with a sufficient thickness on the whole. ○: Slightly brown overall
It is estimated that the film is formed entirely but the film thickness is thin. △ 1: Light brown overall. It is supposed that the film thickness is insufficient. △ 2: The body is slightly brown and the bottom is light brown. Despite the fact that the film was formed in a film, the thickness of the trunk was rather thin and the thickness of the bottom was presumed to be insufficient. It is presumed that the film thickness is thick x1: The body is locally dark brown It is presumed that plasma burning is strong in the body and the film is locally thick x2: No coloring Almost no deposition Inferred

1.3.2. After plasma enhanced chemical vapor deposition, a thin section of the cross section of the plastic container was cut out and observed with a transmission electron microscope (TEM) H7650 manufactured by Hitachi High-Technologies Corporation.
Specifically, the part (A) is divided into three equal parts in the length direction, and is divided into a part (A ₁ ), a part (A ₂ ), a part (A ₃ ) from the opening side to the bottom side, and a part (A) ₁ ) The thickness of the gas barrier film at the center in the length direction is T ₁ , the thickness of the gas barrier film at the center in the length direction of the portion (A ₂ ) is T ₂ , and 3 mm from the bottom end of the portion (A ₃ ). the thickness of the gas barrier film of the above was T ₃ (Fig. 3). Table 1 shows the results.

1.3.3. Gas barrier property Using OX-TRAN2 / 61 manufactured by MOCON, the oxygen permeation rate (cc / pkg / 24h · air) per container at 23 ° C. and 50 RH% was measured. The adapter head for the above device was attached to the container opening, and the measurement was performed. The evaluation criteria were as follows. Table 1 shows the results.
◎: 0.0010 or more and less than 0.0020 ○: 0.0020 or more and less than 0.0030 △: 0.0030 or more and less than 0.0040 ×: 0.0040 or more

As is clear from the results shown in Table 1, T ₁ and T ₂ are 10 nm or more and 100 nm or less, and the ratio of T ₃ to the average thickness T _ave of T ₁ and T ₂ (T ₃ / T _ave ) is 0.4. It was found that when the ratio was more than that, a plastic container having good appearance and gas barrier properties could be obtained.

Also, as is clear from the results shown in Table 1, during plasma enhanced chemical vapor deposition, between the external electrode and the container, along the outer shape of the container, a dielectric was provided on the opening side, and a conductor was provided on the bottom side. continuously arranged, and, around the portion of the container (a), the length of the portion of the length L ₁ of the dielectric from the open end of the (a) up to the conductor portion (a) and 50% to 90% of the portion (a) a bottom end portion length L ₂ of the conductor up to the dielectric from, and 10% to 50% of the length of the portion (a) Thus, it was found that a plastic container having good appearance and gas barrier properties as described above can be manufactured.

2. Examples 4 and 5
2.1. Film forming method and film forming conditions of gas barrier film The same as in Example 1.

2.2. Container A container having a portion (A) was produced by injection blow molding polyethylene terephthalate. In the manufactured container, as shown in FIG. 2 (A), the entire body was made of a portion (A). The inner diameter and length are as shown in Table 2. The bottom was hemispherical.

2.3. Evaluation The same evaluation as in Example 1 was performed. Table 2 shows the results.

  As is clear from the results shown in Table 2, even when the inner diameter of the portion (A) was smaller or the length was longer, a plastic container having good appearance and good gas barrier properties could be produced. From the above, it is considered that similar results are obtained for the portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less.

3. Examples 6 and 7
3.1. Film forming method and film forming conditions of gas barrier film The same as in Example 1. However, around the opening side large diameter portion of the later was placed dielectrics.

3.2. Container A container having a portion (A) was produced by injection blow molding polyethylene terephthalate. The manufactured container had a large-diameter portion on the opening side as shown in FIG. Table 3 shows the inner diameter and length. The bottom was hemispherical.

2.3. Evaluation The same evaluation as in Example 1 was performed. Table 3 shows the results.

  As is clear from the results shown in Table 3, even in the case of having the large diameter portion on the opening side, a plastic container having good appearance and gas barrier properties was able to be produced. It is considered that a similar effect can be obtained even when the bottom-side large-diameter portion is provided.

The oxygen permeability in the above evaluation of the gas barrier property is a value "per container". The oxygen permeability (cc / m ² / 24h · air) per unit area differs depending on the size (inner area) of the container. When the evaluation criteria of ◎, ○, Δ, and × relating to “gas barrier properties” in Tables 1 to 3 are converted into evaluation criteria per unit area, the results are as follows.
In the case of the containers of Examples 1 to 3 and Comparative Examples 1 to 4: ：: 0.32 or more and less than 0.64 ：: 0.64 or more and less than 0.96 Δ: 0.96 or more and less than 1.3 ×: 1.3 As described above, the container of Example 4 ◎: 0.35 or more and less than 0.71 The container of Example 5 ：: 0.11 or more and less than 0.21 The container of Example 6 ６: 0.16 or more Less than 33 In the case of the container of Example 7 ○: 0.14 or more and less than 0.28

  INDUSTRIAL APPLICABILITY The plastic container according to the present invention can be suitably used as a plastic container used for storage and transportation of contents such as medicines, medical supplies, foods, industrial parts, and the like.

DESCRIPTION OF SYMBOLS 1 Opening 2 Body 3 Bottom 11 Dielectric 12 Conductor 15 External electrode 20 Container

Claims (3)

A vacuum chamber having an external electrode and an internal electrode accommodates a non-deposited plastic container inside the external electrode, and the distance between the tip of the internal electrode and the opening of the non-deposited plastic container is 0 mm or more and 30 mm or less. after step as the installation process, forming a gas barrier film on an inner surface of the ungrown plastic container by the plasma chemical vapor deposition, and a film formation step,
The undeposited plastic container has a hollow body extending substantially coaxially, an opening present at one end of the body, and a bottom part closing the other end of the body,
The body has a portion (A) having an inner diameter of 5 mm or more and 20 mm or less and a length of 30 mm or more and 150 mm or less at one location,
The barrel, in its entirety, and the inner diameter of 5mm or more, before Symbol installation process, between the external electrode and the ungrown plastic container, along the contour of the ungrown plastic container, a dielectric on the opening side Body, conductors on the bottom side, continuously arranged,
Around the said portion (A), from the open end of the moiety (A) of the dielectric down to the conductor length L _1, more than 50% of the length of the portion (A) 90 % or less, and the partial the conductor length L ₂ from the bottom end of the (a) up to the dielectric, and 10% to 50% the length of the portion (a),
Manufacturing method of plastic container. The undeposited plastic container may have the opening at one end of the portion (A) or an opening having an inner diameter of more than 20 mm and a length of 100 mm or less between one end of the portion (A) and the opening. A side large diameter portion and the opening is present at one end of the opening side large diameter portion,
  The other end of the portion (A) and the bottom portion are directly integrated, or a bottom portion having an inner diameter of more than 20 mm and a length of 200 mm or less is provided between the other end of the portion (A) and the bottom portion. The method for manufacturing a plastic container according to claim 1, further comprising a diameter portion, wherein the other end of the bottom-side large diameter portion and the bottom portion are directly integrated. The method for producing a plastic container according to claim 1, wherein the gas barrier film is a Si-containing film, a diamond-like carbon film, or an alumina film.

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