JPH10226011A - Transparent barrier film, laminate material using it, and packaging container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve transparency and barrier properties and to improve post- processing suitability to prevent occurrence of crack at the time of post- processing by forming a barrier layer provided at least on one surface of a flexible plastic base material as a non-crystalline thin film of aluminum oxide. SOLUTION: A barrier layer 3 provided at least on one surface of a flexible plastic base material 2 of a transparent barrier film 1 is formed of a non- crystalline thin film 3a of aluminum oxide. In the case of manufacturing the film 1 mainly by a vacuum deposition process, the non-crystalline thin film of aluminum oxide is formed on a flexible plastic base material 113 fed from a winding roll 112 in a vacuum chamber 111 on a cooling coating drum 114 entering into a deposition chamber 115 while injecting oxygen from an oxygen outlet 117 via masks 118, and the material 113 after the thin film is formed is wound on a winding roll 119 and manufactured.

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.

[0003] With respect to a packaging laminate made by laminating aluminum foil as described above, for example, polyvinylidene chloride,
Alternatively, a laminate having a barrier layer made of an ethylene-vinyl alcohol copolymer has been developed and proposed.
However, in the laminate using the above polyvinylidene chloride, since this contains a chlorine atom,
If incineration is performed after use, chlorine gas is generated, which is not preferable in terms of environmental hygiene. Further, in the laminated material using the ethylene-vinyl alcohol copolymer, oxygen permeability is low, and has the advantage of low adsorption of flavor components, but when it comes into contact with water vapor,
There is a problem that the barrier property is remarkably reduced. For this reason, 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. As a result, there is a problem that the manufacturing cost is increased.

Therefore, in recent years, as a barrier laminate having a high barrier property, a stable fragrance retention property and a high transparency, for example, a deposited film of silicon oxide, aluminum oxide or the like is provided. There has been proposed a laminated material using a transparent barrier film having the above configuration. 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. In addition, there is no environmental problem at the time of disposal, and demand for packaging materials and others is 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 the above operations are employed during post-processing such as printing and laminating, cracks are easily generated, and once cracks occur, the barrier properties are significantly reduced. There is a problem that. Further, 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, to increase the thickness of the deposited film Accordingly, on the contrary, cracks and the like are easily generated, 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 cracks are easily generated, and in this case, the same problem as described above occurs. It becomes something. In the above description, the composition of the deposited silicon oxide film is usually SiO _x (X
= 1 to 2). In this case, a deposited film of silicon oxide where X = 2 is completely transparent but has no barrier property, and a deposited film of silicon oxide where X = 1 has a sufficient barrier property. However, there is a problem that the film is colored brown and there is no transparency at all,
For this purpose, usually, a deposited film of silicon oxide in the range of X = 1 to 2 is formed. However, the film is colored yellow-brown, and when this is used as a packaging material, a packaged product is produced. Are inferior in appearance and barrier properties are 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. Furthermore, the deposited film of aluminum oxide, like the deposited film of silicon oxide described above,
It is formed of aluminum oxide represented by AlO _x (X = 0 to 1.5). When X is small, that is, when it is close to aluminum, the barrier property is improved, and the film becomes soft and flexible. Although it has the advantage of being rich, it has the problem that the film is colored brown, and furthermore, because the proportion of aluminum increases, the transparency is poor, and when used for packaging materials, the contents can be visually recognized. Becomes difficult,
There is also a problem that the suitability for a microwave oven is lost, and there is no difference from a conventional deposited film made of aluminum. On the other hand, in the above, conversely, when X increases, the transparency increases, but the vapor-deposited film becomes hard, flexibility, workability, etc. decrease, and furthermore, the barrier properties, particularly, the water vapor barrier properties decrease significantly. There is a problem. 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. Therefore, the present invention has excellent transparency and high barrier properties in view of the above circumstances,
Another 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 a packaging material and the like, a laminated material and a packaging container using the same.

[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)
Wherein the value of X increases in the depth direction from the film surface toward the inner surface of the amorphous thin film of aluminum oxide. Producing a transparent barrier film composed of an amorphous thin film of aluminum, further producing a packaging laminate by laminating a heat-sealing resin layer, a base film layer, etc. on the transparent barrier film, Thereafter, a packaging container is manufactured by bag making or box making using the packaging laminate material, and then, using the packaging container, and filling and packaging various articles, It has excellent transparency and high barrier properties, has no cracks during post-processing, has extremely high post-processing suitability, and has sufficient microwave oven suitability even when packaged products are microwaved. Have various types of packaging materials Transparent barrier film having a packaging suitability for goods, and completed the present invention have found that it is possible to produce a laminated material and packaging container or the like using it.

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 present invention relates to a transparent barrier film comprising an amorphous thin film of aluminum oxide, 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. ), Wherein the value of X increases in the depth direction from the film surface toward 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 made from a bag or a box using the above-described laminated material, 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. The heat-sealable resin layers 4 and 4 located on the innermost layer are prepared so that the surfaces thereof are opposed to each other and are superimposed on each other. Part 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, as the amorphous thin film of aluminum oxide constituting the transparent barrier film according to the present invention, AlO _x (where X is 0.5 to 0.5)
(Representing a number of 1.5). Thus, in the present invention, the above formula AlO _x (where X is 0.5 to 0.5)
An amorphous thin film of aluminum oxide represented by the following formula: AlO _x (where X is 0.5
Represents a number in the range of ~ 1.5. ), Wherein the value of X increases in the depth direction from the film surface toward the inner surface of the amorphous thin film of aluminum oxide. A non-crystalline thin film of aluminum oxide can be used. In the above, as the value of X, basically, a value of X = 0.5 or more can be used, but in the present invention,
When X is less than 1.0, it is desirable to use those having X = 1.0 or more, since coloring is intense, transparency is poor, and there is no microwave oven suitability, and X = 1.5 or more.
Is a state in which aluminum and oxygen are completely oxidized, and therefore, an upper limit of X = 1.5 can be used. Next, in the present invention, the thickness of the amorphous thin film of aluminum oxide is, for example, about 10 to 3000 °, preferably 60 to 3000 °.
It is desirable to arbitrarily select and form within the range of about 1000 °.

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 (where X represents a number in the range of 0.5 to 1.5)
Wherein the value of X increases in the depth direction from the film surface to 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 entry side of the flexible plastic base material 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 oxygen ejection concentration is changed, initially increased, and then gradually decreased. While squirting oxygen. As described above, aluminum or an oxide of aluminum and oxygen are sprayed on the surface of the flexible plastic base material 113 while changing the jetting position or concentration of the oxygen, and the mask 118,
Through 118, a gas of aluminum or aluminum oxide and a gas of oxygen are ejected and vapor-deposited. 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 forming a vapor-deposited film, the aluminum or aluminum oxide gas and oxygen gas interact with each other to form masks 118 and 11.
8, on the surface of the flexible plastic substrate 113,
An amorphous thin film of aluminum oxide in which the value of X increases in the depth direction from the film surface toward the inner surface by forming an amorphous thin film of aluminum oxide. It is.

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 large, and first, a thin film having a large X value of AlO _X is formed. Next, as the flexible plastic substrate further proceeds, it ejects aluminum or an oxide of aluminum while gradually decreasing the proportion of oxygen, where the X value of AlO _X is small. A film is formed. By the method described above, a non-crystalline thin film of aluminum oxide is formed on the surface of the flexible plastic substrate, and the value of X increases in the depth direction from the film surface toward the inner surface. It is possible to form a non-crystalline thin film of aluminum oxide. 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, a crucible and a core.
The non-crystalline thin film of aluminum oxide can be formed by moving the burning drum, tilting the oxygen blowing port, or by various methods.

[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 material constituting the base film is, for example, mechanical, physical, chemical, etc. since it becomes a basic material when constituting a packaging container. In particular, it is possible to use a resin film or sheet having strength, toughness, and heat resistance, and specifically, for example, a polyester resin, polyamide Use resin or polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluororesin, or other tough resin film or sheet, etc. can do. 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 about 5 μm to 100 μm, preferably 10 μm to 50 μm.
The m-th position 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. Note that in the above description, the deposited film of aluminum oxide was formed by changing X = 1.0 to X = 1.5.

Comparative Example 1 Using the vapor deposition machine in the above-mentioned Example 1, the thickness was 12 μm.
Using a biaxially stretched polyethylene terephthalate film as described above, without changing the oxygen concentration, in the same manner as in Example 1 above, as a comparative example, a transparent film having a 300 mm thick aluminum oxide vapor-deposited film A barrier film was manufactured. Note that, in the above, the deposited film of aluminum oxide was formed without changing X at 1.0.

Comparative Example 2 Using the vapor deposition machine of the above-mentioned Example 1, a thickness of 12 μm
Using a biaxially stretched polyethylene terephthalate film as described above, without changing the oxygen concentration, in the same manner as in Example 1 above, as a comparative example, a transparent film having a 300 mm thick aluminum oxide vapor-deposited film A barrier film was manufactured. Note that, in the above description, the deposited film of aluminum oxide was formed without changing X at 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, first, in the case of Example 1, the value of X increased in the depth direction in the case of Example 1. 1 was constant at X = 1.0, and that of Comparative Example 2 was constant at X = 1.5. 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 coloration, transparency, suitability for a microwave oven, and the like, and Comparative Example 2 was inferior in barrier properties, generation of cracks, suitability for post-processing, 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 a non-crystalline thin film of aluminum oxide, wherein the X-value increases in a depth direction from the film surface toward the inner surface. Manufacturing,
A heat-sealing resin layer, a base film layer, and the like are laminated on the transparent barrier film to produce a packaging laminate, and thereafter, the packaging laminate is used to form a bag or a box. The packaging container is manufactured by using the packaging container, and various articles are filled and packaged in the packaging container to have excellent transparency and high barrier properties, and to be cracked during post-processing. Transparent barrier that has extremely high post-processing suitability without the occurrence of any other problems, and has sufficient microwave-operating suitability even when the packaged product is subjected to a microwave oven, and has packaging suitability for various articles as a packaging material. A film, a laminated material and a packaging container using the film can be produced. 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. Further, in the present invention, opacity due to a small X value, deterioration of microwave oven suitability, etc.
The problem is eliminated by reducing the film thickness in the region where the 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 an advantage that cracks and the like are hardly generated on the surface because the film in the region where the X value is small on the surface is soft, and a film having extremely excellent workability can be formed. Especially, in printing, post-processing such as laminating, etc., even if an impact or stress is applied to the surface of the barrier layer, the surface film is soft and no crack is generated.
As a result, no deterioration in barrier properties is observed, 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 (9)

[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. A transparent barrier film, comprising: 2. A non-crystalline thin film of aluminum oxide,
2. The method according to claim 1, wherein the non-crystalline thin film is made of aluminum oxide represented by the formula AlO _x (where X represents a number in the range of 1.0 to 1.5). The transparent barrier film to be described. 3. A compound of the formula AlO _x , wherein X is from 1.0 to 1.
Represents a number in the range of 5. 3. The transparent barrier film according to claim 2, wherein the value of X increases in the depth direction from the film surface to the inner surface of the amorphous thin film of aluminum oxide represented by the formula (3). . 4. At least a flexible plastic substrate and a barrier layer provided on at least one surface of the flexible plastic substrate, and the barrier layer is made of an amorphous thin film of aluminum oxide. A transparent barrier film layer and a heat-sealing resin layer. 5. The laminate according to claim 4, wherein a base film layer is further laminated on the barrier layer side of the transparent barrier film. 6. The laminated material according to claim 4, wherein a base film layer and a heat-sealing resin layer are further laminated on the barrier layer side of the transparent barrier film. 7. A non-crystalline thin film of aluminum oxide,
(Wherein, X represents. A number in the range of 1.0 to 1.5) Formula AlO _X above claim 4, characterized in that it consists of non-crystalline thin film of aluminum oxide which is represented by, 5 or 6
The laminated material described in. 8. A compound of the formula AlO _x , wherein X is 1.0-1.
Represents a number in the range of 5. 8. The amorphous thin film of aluminum oxide represented by the formula (1), wherein the value of X increases in the depth direction from the film surface to the inner surface. The laminated material described in. 9. At least a substrate film layer, a flexible plastic substrate, and a barrier layer provided on at least one surface of the flexible plastic substrate, and the barrier layer is made of aluminum oxide. A packaging material characterized by using a laminated material obtained by sequentially laminating a transparent barrier film layer composed of a crystalline thin film and a heat-sealing resin layer, and then forming this into a bag or a box. container.