JPH10226012A - Transparent barrier film, laminated material and packaging container using the same - Google Patents

Abstract

[PROBLEMS] To have excellent transparency and high barrier properties, and
An object of the present invention is to provide a transparent barrier film having suitability for post-processing, particularly having suitability for a microwave oven, and suitable for packaging materials and the like, a laminated material using the same, and a packaging container. The flexible plastic substrate comprises a flexible plastic substrate and a barrier layer provided on at least one surface of the flexible plastic substrate, and the barrier layer comprises a non-crystalline aluminum oxide thin film. Further, the amorphous thin film of the aluminum oxide has the formula AlO _x (where X is 1.0 to 1.0).
Represents a number in the range of 1.5. A) a non-crystalline thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the film surface to the inner surface. The present invention relates to a transparent barrier film, a laminated material and a packaging container using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent barrier film, a laminated material and a packaging container using the same, and more particularly to a transparent barrier film having excellent transparency and excellent barrier properties against oxygen, water vapor and the like. Has packaging suitability for various goods,
Further, the present invention relates to a transparent barrier film having microwave oven suitability and excellent post-process suitability, and a laminate and a packaging container using the same.

[0002]

2. Description of the Related Art Conventionally, various packaging materials having a barrier property against oxygen, water vapor, etc. have been developed.
Although proposed, the most common is a packaging laminate in which an aluminum foil is laminated on a flexible plastic substrate. This has the advantage that a stable barrier property against oxygen, water vapor, sunlight, etc. can be obtained, but the aluminum foil as a barrier layer is inferior to incineration and is not easy to dispose after use. Having. Furthermore, the above-mentioned laminated material for packaging in which the aluminum foil is laminated has a problem that there is no transparency and a problem that it lacks a microwave oven suitability.

With respect to a packaging laminate made by laminating aluminum foil as described above, a laminate having a barrier layer made of, for example, a polyvinylidene chloride resin or an ethylene-vinyl alcohol copolymer has been developed. Proposed. However, in the laminated material using the above vinylidene chloride-based resin, since it contains chlorine atoms, there is a problem that chlorine gas is generated when incinerated after use, which is not preferable for environmental hygiene. In addition, in the laminate using the above-mentioned ethylene-vinyl alcohol copolymer, although the oxygen permeability is low and the adsorbability of flavor components is low, the barrier property is significantly reduced when contacted with water vapor. Therefore, in order to shield the ethylene-vinyl alcohol copolymer layer as a barrier layer from water vapor,
There is a problem that the laminated structure of the laminated material is complicated, and as a result, there is a problem that the manufacturing cost is increased.

[0004] In recent years, as a barrier laminate having a high barrier property, a stable fragrance retention property and a high transparency, for example, inorganic oxides such as silicon oxide and aluminum oxide are used. Laminated materials using a transparent barrier film having a configuration provided with a vapor-deposited film have been proposed. This material is excellent in transparency and has a high barrier property against oxygen, water vapor and the like as compared with a conventional barrier laminate material using an aluminum foil or the like. Furthermore, there is no environmental problem at the time of disposal, and the demand for packaging materials and the like is greatly expected.

[0005]

However, in the case of a laminated material using the above-mentioned transparent barrier film, since the film itself is inferior in flexibility, if the film is rolled or bent, the vapor deposition film is not formed. Cracks easily occur easily, for example, when performing the above-mentioned operations during post-processing such as printing and laminating, cracks easily occur, and once cracks occur,
There is a problem that the barrier properties are significantly reduced. Also,
In the above-mentioned transparent barrier film, for example, in order to improve the barrier properties, it is often attempted to increase the thickness of the deposited film, in this case, by increasing the thickness of the deposited film, Conversely, cracks and the like tend to occur, and have the same problems as described above. Furthermore,
In the above-mentioned transparent barrier film, when this causes a dimensional change due to moisture absorption, the deposited film is difficult to follow the dimensional change and easily generates cracks. In this case, the same problem as described above occurs. Things. In the above description, the composition of the deposited silicon oxide film is usually SiO 2
_X (X = 1 to 2). In this case, X = 2
Is completely transparent but has no barrier property at all, and a silicon oxide deposited film with X = 1 has a sufficient barrier property, but the film is brownish brown. However, there is a problem that the film is not transparent at all. For this reason, usually, a deposited film of silicon oxide in the range of X = 1 to 2 is formed. When it is colored and used as a packaging material, there is a problem that the appearance of the packaged product is inferior and the barrier property is also inferior. Next, in the above, in the case of a deposited film of aluminum oxide, it is said that the film is transparent as compared with that of silicon oxide, but it is true that aluminum oxide (Al ₂ O ₃ ) obtained by completely oxidizing aluminum is used. The deposited film is colorless and transparent, but this film is very hard and inferior in flexibility as compared with that of silicon oxide, and therefore may be bent during post-processing such as printing and laminating. Then, there is a problem that a crack is easily generated in the film, and the barrier property is remarkably reduced. Further, the deposited film of aluminum oxide is also formed of aluminum oxide represented by AlO _x (X = 0 to 1.5), similarly to the deposited film of silicon oxide described above. When approaching aluminum, the barrier property is improved, the film is also soft, and there is an advantage of being rich in flexibility, but there is a problem that the film is colored brown, and further, since the proportion of aluminum increases, Poor transparency, when used for packaging materials, etc., makes it difficult to see the contents, and also loses microwave oven suitability, and has the problem that it is no different from a conventional aluminum deposited film. . In the above, conversely, when X increases, transparency increases, but the deposited film becomes hard,
There is a problem that workability and the like are reduced, and furthermore, barrier properties, particularly water vapor barrier properties are significantly reduced. At present, in the deposited film of aluminum oxide, the film is formed by using aluminum oxide of X ≒ 1.5, and the barrier property, workability and the like are slightly inferior, but the emphasis is on emphasizing the transparency. The fact is that they use it. In view of the above circumstances, the present invention has excellent transparency and high barrier properties, and has post-processing suitability, and particularly has a microwave oven suitability, and is suitable for a packaging material and the like. It is an object of the present invention to provide a film, a laminated material using the film, and a packaging container.

[0006]

As a result of various studies to solve the above problems, the present inventor has focused on a thin film made of aluminum oxide, and
A barrier layer provided on at least one surface of the flexible plastic substrate, wherein the barrier layer has the formula AlO
_X (wherein, X represents a number in the range of 1.0 to 1.5)
Consists of a non-crystalline thin film of aluminum oxide represented by, further, the non-crystalline thin film of aluminum oxide,
In the depth direction from the film surface to the inner surface, a transparent barrier film made of an amorphous thin film of aluminum in which the value of X in the above formula is decreasing is manufactured. -Tosile resin layer, to produce a packaging laminate by laminating a base film layer, and the like, further, using the packaging laminate to produce a bag or box to produce a packaging container, Thus, when the packaging container was used and filled with various articles, it had excellent transparency and high barrier properties, and had no cracks or the like during post-processing and was extremely high. A transparent barrier film having post-processing suitability, further having sufficient microwave oven suitability even when the packaged product is microwaved, and having packaging suitability for various articles as a packaging material, a laminated material using the same. And can manufacture packaging containers, etc. It is intended that the present invention has been completed and found a.

That is, the present invention comprises a flexible plastic substrate, and a barrier layer provided on at least one surface of the flexible plastic substrate.
The amorphous thin film of aluminum oxide is composed of an amorphous thin film of aluminum oxide, and the amorphous thin film of aluminum oxide is represented by the formula AlO _x (where X represents a number in the range of 1.0 to 1.5). A non-crystalline thin film of aluminum oxide represented by X in the depth direction from the film surface to the inner surface.
The present invention relates to a transparent barrier film comprising an amorphous thin film of aluminum oxide having a reduced value of, a laminated material and a packaging container using the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of the transparent barrier film according to the present invention, a laminated material and a packaging container using the transparent barrier film will be described with reference to the drawings by exemplifying a few examples. FIGS. 1, 2 and 3 show the present invention. And FIG. 4, FIG. 5, and FIG. 6 are cross-sectional views showing a layer structure of a laminated material manufactured using the above-described transparent barrier film according to the present invention. And
FIGS. 7, 8, 9, 10 and 11 are plan views showing the configuration of a packaging container made from a bag or a box using the laminated material using the transparent barrier film according to the present invention. FIG.

The transparent barrier film 1 according to the present invention comprises:
As shown in FIG. 1, a flexible plastic substrate 2 and a barrier layer 3 provided on at least one surface of the flexible plastic substrate 2 are further provided. It is characterized by being composed of a crystalline thin film 3a, and has a basic configuration. The transparent barrier film according to the present invention will be described in further detail with reference to FIG.
The amorphous thin film 3a of aluminum oxide shown in FIG.
Non-crystalline aluminum oxide thin film 3 represented by lOX (where _X represents a number in the range of 1.0 to 1.5)
b) a transparent barrier film 1a. Furthermore, the transparent barrier film according to the present invention, as shown in FIG. 3, a thin film 3b of the non-crystalline aluminum oxide shown in FIG. 2 described above, the formula AlO _X (wherein, X
Represents a number in the range of 1.0 to 1.5. ), And the value of X decreases in the depth direction from the film surface to the inner surface of the amorphous thin film of aluminum oxide. A transparent barrier film 1b composed of an amorphous thin film 3c of aluminum oxide can be given. The above examples illustrate a few examples of the transparent barrier film according to the present invention, and are not limited thereto. For example, although not shown, as an amorphous thin film of aluminum oxide, a flexible film may be used. It may be one provided on not only one surface but also both surfaces of the conductive plastic substrate layer.

Next, a description will be given of a few examples of the laminated material manufactured using the transparent barrier film according to the present invention. The laminated material according to the present invention is, for example, as shown in FIG. The amorphous thin film 3 of aluminum oxide of the transparent barrier film shown in FIGS.
(3a, 3b, 3c), at least a heat sink
And a laminated material A obtained by laminating the conductive resin layers 4. Further, as a laminated material according to the present invention, as shown in FIG. 5, at least a substrate film layer 5 is laminated on the surface of the flexible plastic substrate 2 of the laminated material A shown in FIG. Laminated material B can be used. Alternatively, as a laminated material according to the present invention, as shown in FIG. 6, at least a heat-sealing resin layer 4a is laminated on the surface of the base material film layer 5 of the laminated material B shown in FIG. Laminated material C. Thus, the above-mentioned examples are a few examples constituting the laminated material according to the present invention, and are not limited thereto. For example, in the present invention, although not shown, a base film Layer, heel
In addition to the sealing resin layer and the like, it is possible to design and manufacture various types of laminated materials by arbitrarily laminating other base materials according to the purpose of use and application. .

Next, in the present invention, the structure of the packaging container according to the present invention, which is formed by using the above-described laminated material to form a bag or box, will be described. By way of example, a description will be given of a packaging container made from a bag or a box using the laminated material B shown in FIG. 5. As shown in a perspective view of FIG. 7, two laminated materials B and B are prepared. Then, the heat-sealing resin layers 4, 4 located at the innermost layer are superposed on each other so that the surfaces thereof face each other, and then the three sides of the outer peripheral edge are heat-sealed to form a seal portion. 6,
By forming 6 and 6, the three-way seal type flexible packaging container D according to the present invention can be manufactured.

Next, as a packaging container according to the present invention, as shown in the plan view of FIG.
First, a predetermined crease l is used.
(Shown by a dotted line), a blank plate 8 for forming a paper container having a sticking portion 7 and the like is manufactured by punching, and then, as shown in a perspective view of FIG. The attachment portion 7 is overlapped with the other side end portion 9 (shown in FIG. 8), and the overlapped portion is heat-sealed to form a side end seal portion 10 to produce a body portion 11. The lower portion of the body 11 is folded in a conventional manner and heat-sealed to form a bottom portion 12.
Further, the upper portion is heat-sealed according to a conventional method to form the roof-type seal portion 13, whereby the roof-type paper packaging container E according to the present invention can be manufactured.

Further, as the packaging container according to the present invention, as shown in the plan view of FIG. 10, for example, the above-mentioned laminated material C shown in FIG. 6 is used.
A blank plate 8a for forming a rectangular paper container, which is capable of forming a cylindrical body, is manufactured by stamping and then, as shown in the perspective view of FIG. The attachment portion 7a is overlapped with the other side end portion 9a (shown in FIG. 10), and the overlapped portion is heat-sealed to form a side end seal portion 10a.
Is formed to produce a cylindrical body 11a, and further, for example, a cylindrical bottom plate 14 is mounted on a lower portion of the cylindrical body 11a.
A bottom seal portion 15 is formed by sealing to form a bottom portion 14a. Further, a cylinder having a drinking port 17 sealed with a peeling piece 16, for example, in the upper portion of the cylindrical container 11a. The upper cover portion 19 is formed by heat-sealing the lid 18 in the shape of a letter, and the lid 18a is formed to manufacture the cylindrical paper can-shaped packaging container F according to the present invention. it can.
In the present invention, it is needless to say that the present invention is not limited to the above-illustrated packaging container, and that various types of packaging containers can be manufactured depending on the purpose, application, and the like. Needless to say.

Next, in the present invention, the materials constituting the transparent barrier film, laminated material, packaging container and the like according to the present invention as described above will be described. As such materials, various materials can be used. it can. First, in the present invention, the material constituting the transparent barrier film according to the present invention will be described. First, as a flexible plastic substrate, a plastic film or sheet capable of holding an amorphous thin film of aluminum oxide is used. Any material can be used as long as it is, for example, polyethylene, polypropylene, polyolefin resin such as polybutene, (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinylidene chloride resin, Saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin, etc. Various resin films or sheets can be used. These resin films or sheets may be stretched in a uniaxial or biaxial direction, and have a thickness of about 10 to 200 μm, preferably 10 to 10 μm.
About 0 μm is desirable. If necessary, the film or sheet of the resin may be coated with an anchor coat agent or the like and subjected to a surface smoothing treatment or the like.

Next, in the present invention, the transparency according to the present invention will be described.
Amorphous aluminum oxide constituting bright barrier film
The thin film of the formula AlO_x(Where X is 0.5 to
Of aluminum oxide represented by the following formula:
A crystalline thin film can be used. Thus, the present invention
In the above, the formula AlO_x(Where X is 0.5 to
Of aluminum oxide represented by the following formula:
As a crystalline thin film, the formula AlO _X(Where X is 0.5
Represents a number in the range of ~ 1.5. Aluminum oxide represented by)
An amorphous thin film of aluminum, further comprising
Amorphous thin film goes from the film surface to the inner surface
Aluminum oxide whose value of X decreases in the depth direction
Can be made of an amorphous thin film of
Wear. In the above, the value of X is basically X
= 0.5 or more can be used.
In, when X is less than 1.0, coloring is intense,
In addition, since the transparency is inferior, those having X = 1.0 or more
It is desirable to use
Aluminum and oxygen are completely oxidized
Therefore, use an upper limit of up to X = 1.5.
Can be used. Next, in the present invention,
The thickness of the amorphous thin film of minium is, for example, 1
0-3000 °, preferably 60-1000 °
It is desirable to select and form arbitrarily within the range.

Next, a method of forming an amorphous thin film of aluminum oxide on a flexible plastic substrate in the present invention will be described.
For example, a vacuum deposition method, a sputtering method, an ion press
Physical vapor deposition method (Physical V
apor Deposition method, PVD method), or a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
Vapor Deposition method, CVD method) and the like. In the present invention, when producing a transparent barrier film used for a packaging material, a vacuum deposition method is mainly used, and a plasma chemical vapor deposition method is also partially used. A specific example is shown in FIG.
1 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine. As shown in FIG. 12, the flexible plastic substrate 113 unwound from the unwinding roll 112 in the vacuum chamber 111 passes through the coating drum 114 and enters the vapor deposition chamber 115. Here, the heated aluminum or aluminum oxide as an evaporation source is evaporated in the crucible 116, and at that time,
While blowing oxygen from the oxygen blowing port 117, an amorphous thin film of aluminum oxide is formed on the flexible plastic substrate 113 on the cooled coating drum 114 via masks 118, 118. The transparent barrier film according to the present invention can be manufactured by forming a film and then winding the flexible plastic substrate 113 on which the amorphous thin film of aluminum oxide is formed on a winding roll 119.

Thus, in the present invention, at least one surface of the flexible plastic substrate is provided with the above formula AlO
_X (wherein, X represents a number in the range of 1.0 to 1.5)
Wherein the value of X decreases in the depth direction from the film surface toward the inner surface of the amorphous thin film of aluminum oxide. Specifically, a method of forming an amorphous thin film of aluminum oxide will be described with reference to FIG.
FIG. 3 is a schematic configuration diagram in which a part of a non-crystalline thin film of aluminum oxide is specifically formed using the take-up type vapor deposition machine shown in FIG. In the present invention, as shown in FIG. 13, first, a vacuum chamber (not shown)
The flexible plastic substrate 113 unwound from an unwinding roll (not shown) is
Through the singing drum 114 and into the deposition chamber-115. Next, the heated aluminum or aluminum oxide as an evaporation source is evaporated on the surface of the flexible plastic base material 113 sent into the evaporation chamber-115 in the crucible 116 as described above.
At this time, an amorphous thin film of aluminum oxide is formed through the masks 118 and 118 while blowing oxygen from the oxygen blowing port 117. The positional relationship between the oxygen outlet 117 and the crucible 116 and the oxygen outlet 11 are adjusted.
7 is shifted from the center line i, the crucible 116 is positioned at the center line i, and the oxygen outlet 117 is shifted from the center line i toward the discharge side of the flexible plastic substrate 113. And Thus, the positional relationship as described above in the state, an aluminum heated as the vapor source crucible 116 or aluminum oxide is evaporated, and the area surrounded by the radiation H ₁ Aluminum or aluminum, Spout the oxide. On the other hand, aluminum,
Or while spouting aluminum oxide,
Oxygen is ejected from the oxygen outlet 117 into the area surrounded by the radiation H ₂ , so that when oxygen is ejected, the concentration of oxygen ejected is changed, and the oxygen concentration is initially decreased and then gradually increased. While squirting oxygen. As described above, aluminum, or aluminum oxide and oxygen, while changing the oxygen ejection position or its concentration,
A mask 11 is provided on the surface of the flexible plastic substrate 113.
A gas of aluminum or an oxide of aluminum and a gas of oxygen are ejected and vapor-deposited through 8, 118.
By the way, as described above, a gas of aluminum or an oxide of aluminum and a gas of oxygen are ejected onto the surface of the flexible plastic base material 113 and vapor-deposited, and thus the surface of the flexible plastic base material 113 is formed. When a deposited film is formed, the aluminum or an oxide gas of aluminum and a gas of oxygen interact with each other to form a mask 118,
Via 118, a non-crystalline thin film of aluminum oxide is formed on the surface of the flexible plastic substrate 113,
An amorphous thin film of aluminum oxide in which the value of X decreases in the depth direction from the film surface to the inner surface can be formed.

In the above, aluminum or an oxide of aluminum can be used as a vapor deposition source, as well as a mixture of both. In the above, aluminum, or radiation H ₁ ejection oxide and oxygen aluminum, it has been illustrated schematically to eject radiation H ₂ spreads radially, which, of course, radiation H _1, radiation Rather than the presence of aluminum or aluminum oxide gas and oxygen gas only in the H ₂ region,
Actually, it is considered that the gas is ejected radially with a concentration distribution. Further, in the above, the flexible plastic substrate proceeds in the direction of arrow P, and a non-crystalline thin film of aluminum oxide is formed in a region between the masks. ,aluminum,
Alternatively, while ejecting aluminum oxide, the film passes through a region where the proportion of oxygen is small, and first, a thin film having a small X value of AlO _X is formed. Next, the flexible plastic substrate further forms a film having a large X value of AlO _{X when} jetting aluminum or aluminum oxide while gradually increasing the proportion of oxygen as it proceeds. Turns into a film. By the method described above, a non-crystalline thin film of aluminum oxide is formed on the surface of the flexible plastic substrate, and X is formed in the depth direction from the film surface to the inner surface.
Can form an amorphous thin film of aluminum oxide in which the value of (a) is reduced. As described above, the method of shifting the positional relationship between the crucible and the oxygen outlet is one example, and other methods include, for example, moving the crucible and the coating drum, tilting the oxygen outlet, and various other methods. A non-crystalline thin film of aluminum oxide can be formed.

[0019] In the above deposition machine, vacuum chamber - as the degree of vacuum, 10 ⁰ to 10 ^-5 mbar position, preferably, it is desirable 10 ^-1 to 10 ^-4 mbar position. In addition, the degree of vacuum of the deposition chamber is as follows before oxygen introduction.
10 ⁻² to 10 ⁻⁸ mbar, preferably 10 ⁻³ to 10 mbar
^-7 mbar is desirable, and after oxygen introduction, 1
0 ^-1 to 10 ^-6 mbar, preferably 10 ^-2 to 10 ^-5
Next, the transfer speed of the flexible plastic substrate is preferably 1 mbar.
0 to 800 m / min, preferably 50 to 600 m / min. The amount of oxygen introduced and the like vary depending on the size of the vapor deposition machine and the like.

Next, in the present invention, the innermost layer of the laminated material,
Alternatively, as the heat-sealing resin constituting the heat-sealing resin layer forming the outermost layer, a resin film or sheet which can be melted by heat and fused to each other can be used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer Polymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-
Methyl methacrylate copolymer, ethylene-propylene copolymer, methyl pentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid,
Acid-modified polyolefin resin modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, etc., polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, and other resins. Film or sheet
Can be used. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film, film or sheet is 5 μm to 30 μm.
0 μm is preferable, and more preferably, 10 μm to 100 μm.
μm is desirable.

Next, in the present invention, the base film constituting the base film layer is, for example, a basic material in the case of forming a packaging container. , Etc., having excellent properties, and in particular, a resin film or sheet having strength, toughness, and heat resistance can be used,
Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polyolefin resin,
A film or sheet of a tough resin such as a polycarbonate resin, a polystyrene resin, a polyacetal resin, a fluorine resin, or the like can be used. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is 5μm
To about 100 μm, preferably 10 μm to 50
μm is desirable. In the present invention, the base film as described above is subjected to, for example, front printing or back printing by printing a desired printing pattern such as a character, a figure, a symbol, a picture, or a pattern by a normal printing method. It may be.

Next, in the present invention, as the material constituting the base film, for example, various paper base materials constituting a paper layer can be used. As the paper base material, the base material is provided with moldability, bending resistance, rigidity and the like. For example, strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard , A paper substrate such as processed paper, and the like can be used. In the above, as the paper base material constituting the paper layer, it is desirable to use a base material having a basis weight of about 80 to 600 g / m ² , preferably a base weight of about 100 to 450 g / m ² . Needless to say, in the present invention, a paper base constituting the paper layer and various resin films or sheets as the base films mentioned above can be used in combination.

Next, in the present invention, as a material constituting the laminated material according to the present invention, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene having a barrier property against water vapor, water, etc. Density polyethylene, polypropylene, film or sheet of resin such as ethylene-propylene copolymer, or, oxygen, polyvinylidene chloride having a barrier property against water vapor, etc.,
Film or sheet of resin such as polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, light-shielding obtained by adding a colorant such as pigment to the resin and other desired additives and kneading to form a film. Various colored resin films or sheets having properties can be used. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but usually 5 μm to 300 μm.
And more preferably about 10 μm to 100 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet can be used in any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Next, a method of manufacturing a laminated material using the above-mentioned materials in the present invention will be described. As the method, a conventional packaging material is laminated.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film, and for example, an isocyanate-based (urethane) Series), polyethyleneimine series, polybutadiene series, organic titanium series etc.
Known pretreatments such as coating agents or adhesives for laminating such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., anchor coating Agents, adhesives and the like can be used.

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using the laminated material manufactured in such a manner, the heat-sealing film of the inner layer is opposed to the surface, and the heat-sealing film is folded, or the two sheets are overlapped, and the peripheral edge is further heated. -A bag can be formed by sealing and providing a seal portion. Thus, as a bag-making method, the above-mentioned laminated material is bent with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further sealed with, for example, a side sheet. Seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seal type),
Heat seals such as pleated seal type, flat bottom seal type, square bottom seal type, etc., to form packaging containers of various forms according to the present invention. Can be manufactured. In addition, for example, a self-standing packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the above-described laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotating roll seal,
It can be carried out by a known method such as a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal, and the like. In the present invention, a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container containing a paper substrate as the packaging container, for example, a laminated material in which a paper substrate is laminated is produced as a laminated material, and a desired paper container is produced therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head and the like are manufactured using the blank plate to manufacture, for example, a liquid paper container of a brick type, a flat type or a gable-top type. be able to. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

In the present invention, the packaging container manufactured as described above can be used for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other articles. It is used for filling and packaging.

[0029]

(Evaporation conditions)

Heating method of vapor deposition machine: Electron beam heating method Material: Aluminum Vacuum degree in vacuum chamber: 2 × 10 ⁻³ mbar Vacuum degree of vapor deposition chamber before oxygen introduction: 2 × 10 ⁻⁵ mb
ar Degree of vacuum in the deposition chamber after introducing oxygen: 3 × 10 ⁻⁴ mb
ar Film transport speed: 400 m / min Further, in the above, by changing the film transport speed, the amount of oxygen introduced, the position of the oxygen outlet, etc., a transparent barrier film having a different thickness, oxidation degree, and oxidation degree distribution can be obtained. Manufactured. In the transparent barrier film described above, the X value of aluminum oxide constituting the deposited film of aluminum oxide was reduced from X = 1.5 to X = 1.0.

Comparative Example 1 Using the vapor deposition machine in the above-mentioned Example 1, the thickness was 12 μm.
A biaxially stretched polyethylene terephthalate film was used in the same manner as in Example 1 except that the oxygen concentration was not changed. As a comparative example, a transparent film having a deposited aluminum oxide film having a thickness of 1000 mm was prepared. A barrier film was manufactured. In the transparent barrier film, the X value of the aluminum oxide constituting the aluminum oxide vapor-deposited film was not changed at X = 1.0.

Comparative Example 2 Using the vapor deposition machine of the above-mentioned Example 1, a thickness of 12 μm
A biaxially stretched polyethylene terephthalate film was used in the same manner as in Example 1 except that the oxygen concentration was not changed. As a comparative example, a transparent film having a deposited aluminum oxide film having a thickness of 1000 mm was prepared. A barrier film was manufactured. In the above-mentioned transparent barrier film, the X value of aluminum oxide constituting the deposited film of aluminum oxide was not changed at X = 1.5.

Experimental Example 1 The transparent barrier films produced in Example 1 and Comparative Examples 1 and 2 were evaluated for the following items. (1). The degree of oxidation (X
Value) This was measured with a photoelectron spectrometer (referred to as ESCA). (2). This was measured with a scanning electron microscope. (3). Oxygen Permeability This was measured under the conditions of 23 ° C. and 90% RH with an oxygen permeability measuring device (model name, OXTRAN) manufactured by MOCON, USA. (4). Moisture Permeability This was measured under the conditions of 40 ° C. and 90% RH with a moisture permeability measuring device (model name, PERMATRAN) manufactured by MOCON, USA. (5). Color This was measured in terms of visual color and transmittance at 500 nm. (6). Extensibility The transparent barrier film is pulled by 4% with a tensile tester, and held in that state for 30 seconds. Then, it was returned to the original state and the surface state (crack) was observed with an optical microscope and a scanning electron microscope. At the same time, oxygen permeability and moisture permeability were also measured. (7). Converting aptitude This is because the thickness of the transparent barrier film is 1
A 2-μm biaxially stretched polyethylene terephthalate film was dry-laminated, and then the laminated film was measured for oxygen permeability and moisture permeability. (8). Suitability for microwave oven The transparent barrier film was placed in a microwave oven, and the state was observed. The results of the above evaluation tests are shown in Table 1 below.

[0033]

[Table 1]

As is clear from the results of the evaluation test shown in Table 1 above, in the case of the X value, the value of
X decreases from 1.5 to X = 1.0 in the depth direction. In Comparative Example 1, X = 1.0, and in Comparative Example 2, X = 1.5 is constant. there were. Next, the product of Example 1 was excellent in oxygen permeability, moisture permeability, occurrence of cracks, suitability for post-processing and the like, and also excellent in transparency and the like. Comparative Example 1 was inferior in coloring, transparency, microwave oven suitability, and the like, and Comparative Example 2 was inferior in barrier properties, crack generation, post-processing suitability, and the like.

Example 2 A 5% solution of a two-component curable polyester resin was used as a primer on the vapor-deposited surface of the transparent barrier film produced in Example 1 and coated to a thickness of 1 μm. Then, low-density polyethylene was used on the surface of the coating film, which was extruded and coated to a thickness of 60 μm to produce a laminate according to the present invention having the following layer constitution. Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a vapor-deposited film of aluminum oxide having a thickness of 300 ° / a primer agent layer having a thickness of 1 μm / a low-density polyethylene layer having a thickness of 60 μm. Under the condition of 90% RH, an oxygen permeability measuring device [model name, OXTRAN] manufactured by MOCON, USA
As a result of measuring the oxygen permeability using, the oxygen permeability is
It was 0.3 cc / m ² · day. Further, the above-prepared laminated material was steamed at 40 ° C. and 90% RH using a moisture permeability measuring device (model name, PERMATRAN) manufactured by MOCON, USA. As a result of measuring the permeability, the water vapor permeability was found to be 0.1%.
It was 3 g / m ² · day. Using the laminated material manufactured as described above, a plastic bag was manufactured by bag making with a bag making machine. The plastic bag had a high level of barrier properties, and the barrier properties were not deteriorated. .

Example 3 On the vapor-deposited surface of the transparent barrier film produced in Example 1,
Using a primer agent consisting of a 5% solution of a two-component curable polyester resin, coating this to a film thickness of 1 μm,
Next, low-density polyethylene was used on the coating film surface, and was extruded to 80 μm and coated. Furthermore,
On the biaxially stretched polyethylene terephthalate film surface of the transparent barrier film, low-density polyethylene was used, and this was extruded to a thickness of 100 μm and laminated.
A laminated material according to the present invention having the following layer constitution was produced. 100 μm thick low density polyethylene layer / 12 μm thick
Bi-stretched polyethylene terephthalate film, thickness 3
00 ° deposited aluminum oxide film / primer layer 1 μm thick / low-density polyethylene layer 80 μm thick For the laminates produced above, at 23 ° C. and 90% RH, Mocon, USA Oxygen Permeability Analyzer [Model name, OXTRAN]
As a result of measuring the oxygen permeability using, the oxygen permeability is
It was 0.3 cc / m ² · day. Further, the above-prepared laminated material was steamed at 40 ° C. and 90% RH using a moisture permeability measuring device (model name, PERMATRAN) manufactured by MOCON, USA. As a result of measuring the permeability, the water vapor permeability was found to be 0.1%.
It was 3 g / m ² · day. Using the laminated material produced above, first, the laminated material is rolled, and the overlapped edge thereof is heat-welded to produce a tubular body for forming a tube. A neck was formed at one end by injection molding using polypropylene, and a cap was screwed onto the neck to produce a tube container. Then
The contents were filled from the other opening of the above tube container, and then the opening was heat-sealed to produce a tube-shaped packaged product. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

Example 4 A primer consisting of a 5% solution of a two-component curable polyester resin was used on the vapor-deposited surface of the transparent barrier film produced in Example 1 above, and this was coated to a film thickness of 1 μm. Then, low-density polyethylene was used on the surface of the coating film, which was co-extruded to 80 μm and coated. Next, while extruding a low-density polyethylene with a thickness of 30 μm on the surface of the biaxially stretched polyethylene terephthalate film of the transparent vapor-deposited barrier film, a paper having a basis weight of 200 g / m ² was extruded using a sandwich method. Then, a high-pressure low-density polyethylene was extruded to a thickness of 30 μm on the surface of the paper and laminated to produce a laminated material having the following structure. Low-density polyethylene layer having a thickness of 30 μm / basis weight 200 g /
m ² of the paper layer / thickness of 30μm low density polyethylene layer / thickness of 12μm of the secondary oriented polyethylene terephthalate - Tofirumu Thickness 300Å deposited film / thickness of 1μm primer of silicon oxide - agent layer / thickness of 80μm of Low-density polyethylene layer For the laminated material produced above, an oxygen permeability measuring device [model name, OXTRAN] manufactured by MOCON, USA, under the conditions of 23 ° C. and 90% RH.
As a result of measuring the oxygen permeability using, the oxygen permeability is
It was 0.2 cc / m ² · day. Further, the above-prepared laminated material was steamed at 40 ° C. and 90% RH using a moisture permeability measuring device (model name, PERMATRAN) manufactured by MOCON, USA. As a result of measuring the permeability, the water vapor permeability was found to be 0.1%.
It was 2 g / m ² · day. Using the laminated material manufactured above, first, a blank plate for forming a paper container is manufactured from the laminated material, and the overlapping edge portion is thermally welded using the blank plate to form a square body for forming the paper container. Then, one bottom of the square body was folded and sealed to form a bottom, thereby producing a paper container. Next, the contents are filled from the opening above the paper container, and then the opening is heat-sealed to form a roof-type upper seal, thereby producing a packaged product. did. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

[0038]

As is apparent from the above description, the present invention focuses on a thin film made of aluminum oxide and provides a flexible plastic substrate and at least one surface of the flexible plastic substrate. A barrier layer, wherein the barrier layer is a non-crystalline thin film of aluminum oxide represented by the formula AlO _X (where X represents a number in the range of 1.0 to 1.5); And a transparent barrier film comprising an amorphous thin film of aluminum oxide wherein the value of X decreases in a depth direction from the film surface to the inner surface. And further forming a heat-sealing resin layer on the transparent barrier film,
Laminating the base film layers and the like to produce a packaging laminate, and then producing a packaging container by using the packaging laminate to make a bag or box, and thereby producing the packaging container. Use a container,
Filled and packed with various articles, it has excellent transparency and high barrier properties, and has no post-processing cracks, has extremely high post-processing suitability. Even in a microwave oven, it is possible to produce a transparent barrier film having sufficient microwave aptitude and a packaging aptitude for various articles as a packaging material, a laminated material and a packaging container using the same. That is. That is, in the present invention, a composition having a small X value to a large X value of AlO _X is contained in one layer, so that a film having each characteristic can be formed. For example, a film in a region with a small X value has a high barrier property and excellent processability, and a film in a region with a large X value has excellent transparency and microwave oven suitability. By gradiently changing the composition in the film, a film having any characteristic can be formed. In the present invention, opacity due to a small X value, deterioration of microwave oven suitability, and the like,
The problem is eliminated by reducing the film thickness in the region where the X value is small. Furthermore, in the present invention, the barrier property is deteriorated due to a large X value because a region where the X value is small on the surface of the barrier layer has a high barrier property. By coexisting, a film having excellent barrier properties can be formed without deteriorating the barrier properties of the entire aluminum oxide thin film. Furthermore, in the present invention, the thin film of aluminum oxide has a small X value and a soft film in a portion close to the base material, so that it acts as an interference material and has the advantage that cracks do not occur. Even if a crack is generated on the surface, the portion having a small X value is soft, so that the crack does not propagate and the barrier property does not deteriorate. Therefore, it is possible to form a film which is extremely processable, and in particular, cracks do not occur in printing, post-processing such as laminating, and as a result,
Deterioration of barrier properties and the like are not recognized, and a barrier film having extremely good post-processing suitability can be formed.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a layer configuration of a transparent barrier film according to the present invention.

FIG. 2 is a cross-sectional view illustrating a layer configuration of a transparent barrier film according to the present invention.

FIG. 3 is a cross-sectional view illustrating a layer configuration of a transparent barrier film according to the present invention.

FIG. 4 is a cross-sectional view showing a layer structure of a laminated material manufactured using the above-described transparent barrier film according to the present invention.

FIG. 5 is a cross-sectional view showing a layer structure of a laminated material manufactured using the above-mentioned transparent barrier film according to the present invention.

FIG. 6 is a cross-sectional view showing a layer structure of a laminated material manufactured using the above-described transparent barrier film according to the present invention.

FIG. 7 is a perspective view showing a configuration of a packaging container formed from a bag or a box using the laminate using the transparent barrier film according to the present invention.

FIG. 8 is a plan view showing a configuration of a packaging container formed by bag making or box making using a laminated material using the transparent barrier film according to the present invention.

FIG. 9 is a perspective view showing a configuration of a packaging container made from a bag or a box using the laminated material using the transparent barrier film according to the present invention.

FIG. 10 is a plan view showing a configuration of a packaging container made from a bag or a box using the laminated material using the transparent barrier film according to the present invention.

FIG. 11 is a perspective view showing a configuration of a packaging container made from a bag or a box using the laminated material using the transparent barrier film according to the present invention.

FIG. 12 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine.

FIG. 13 is a schematic configuration diagram in which a part of an evaporator for forming a non-crystalline thin film of aluminum oxide using the take-up evaporator shown in FIG. 12 is specifically enlarged.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Transparent barrier film 1a Transparent barrier film 1b Transparent barrier film 2 Flexible plastic base material 3 Barrier layer 3a Non-crystalline thin film of aluminum oxide 3b Formula AlO _X (where X is 1.0 to 1.5) 3c is an amorphous thin film of aluminum oxide represented by the formula: AlO _x (where X represents a number in the range of 1.0 to 1.5). A non-crystalline thin film of aluminum, wherein the non-crystalline thin film of aluminum oxide further increases the value of X in the depth direction from the surface to the inner surface; Thin film 4 Heat-sealing resin layer 4a Heat-sealing resin layer 5 Base film layer 6 Seal part 7 Adhesion part 8 Blank plate for forming paper container 9 Side end 10 Side end seal 11 11 torso 12 bottom 13 roof Mold seal part 7a Sticking part 8a Blank plate for paper container formation 9a Side end part 10a Side end seal part 11a Cylindrical trunk part 11a 14 Cylindrical bottom plate 14a Bottom part 15 Bottom seal part 16 Peel off Piece 17 Drinking port 18 Cylindrical lid plate 18a Lid part 19 Upper seal part 111 Vacuum chamber 112 Unwinding roll 113 Flexible plastic substrate 114 Coating drum 115 Vapor deposition chamber 116 Crucible 117 Oxygen blowing Mouth 118 Mask 119 Winding roll A Laminated material B Laminated material C Laminated material D Three-way seal type soft packaging container E Roof type paper packaging container F Cylindrical paper can packaging container H ₁ Radiation H ₂ Radiation P Arrow l Folded line i Center line

Claims (7)

[Claims] 1. A flexible plastic base material comprising: a flexible plastic base material; and a barrier layer provided on at least one surface of the flexible plastic base material, wherein the barrier layer comprises a non-crystalline aluminum oxide thin film. In addition, the amorphous thin film of the aluminum oxide has the formula AlO _x (where X is 1.0 to 1.0).
Represents a number in the range of 1.5. A) a non-crystalline thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the film surface to the inner surface. A transparent barrier film, characterized in that: 2. A flexible plastic base material comprising: a flexible plastic base material; and a barrier layer provided on at least one surface of the flexible plastic base material, wherein the barrier layer is formed of an amorphous thin film of aluminum oxide. And the amorphous thin film of aluminum oxide has the formula AlO _x (where X is
Represents a number in the range of 1.0 to 1.5. A) a non-crystalline thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the film surface to the inner surface. A laminated material characterized by laminating a transparent barrier film layer and a heat-sealing resin layer. 3. The non-barrier layer side of a transparent barrier film,
3. The laminated material according to claim 2, further comprising a substrate film layer laminated. 4. The non-barrier layer side of a transparent barrier film,
3. The laminated material according to claim 2, further comprising a substrate film layer and a heat-sealing resin layer laminated. 5. At least a flexible plastic substrate and a barrier layer provided on at least one surface of the flexible plastic substrate, wherein the barrier layer is a non-crystalline thin film of aluminum oxide. And the amorphous thin film of aluminum oxide has the formula AlO _x (where X is
Represents a number in the range of 1.0 to 1.5. A) a non-crystalline thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the film surface to the inner surface. A packaging container characterized by using a laminated material obtained by laminating a transparent barrier film layer and a heat-sealing resin layer, and then forming the bag or box. 6. The non-barrier layer side of a transparent barrier film,
The packaging container according to claim 5, further comprising a base film layer laminated. 7. The non-barrier layer side of a transparent barrier film,
The packaging container according to claim 5, further comprising a base film layer and a heat-sealing resin layer laminated on each other.