JP2001138431A - Transparent barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent barrier film having excellent transparency and high barrier properties even if a polyamide resin film is used as a base material film for vapor deposition, having post-processing properties, especially having microwave oven suitability and suitable for a packaging material and a laminated material using the same. SOLUTION: A transparent barrier film consists of a polyamide resin film and the barrier layer provided on at least one surface of the polyamide resin film. The barrier layer comprises a non-crystalline membrane composed of aluminum oxide which is represented by general formula AlOX (wherein X is a number of 1.0-1.5) of which the value of X is reduced from the surface of the membrane to the interior thereof. A laminated material is obtained by using this transparent barrier film.

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 and a laminated material using the same, and more particularly to a transparent film having excellent transparency and excellent barrier properties for preventing permeation of oxygen, water vapor and the like. The present invention relates to a transparent barrier film having packaging suitability for various articles, further having microwave oven suitability, and excellent post-processing suitability, and a laminated material using the same.

[0002]

2. Description of the Related Art Conventionally, various packaging materials having a barrier property for preventing permeation of oxygen, water vapor and the like have been developed and proposed, but the most common ones are as follows.
Aluminum foil or its vapor-deposited film is known. Further, as a packaging material having a barrier property, such as a resin film, for example, a barrier layer composed of a polyvinylidene chloride resin or an ethylene-vinyl alcohol copolymer has been developed and proposed. . Furthermore, in recent years,
Has high barrier properties and exhibits stable fragrance retention,
Further, as a packaging material having a barrier property rich in transparency, for example, a transparent barrier film having a configuration in which a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a plastic substrate is proposed. Have been. The packaging material having barrier properties as described above is arbitrarily laminated with other plastic films, paper base materials, and other materials to produce a desired packaging laminate, and then used Bags or boxes are used to manufacture packaging containers of various forms, and then used to fill and package a wide variety of articles, including foods and beverages. is there.

[0003]

However, for example, in the above-mentioned aluminum foil or its vapor-deposited film, the barrier property of preventing permeation of oxygen, water vapor and the like is extremely excellent, and furthermore, it blocks sunlight and the like. Although having advantages, aluminum foil or a vapor-deposited film thereof as a packaging material having a barrier property has a problem that it is inferior in incineration suitability and is not easy to dispose after use. Furthermore, the above-mentioned aluminum foil or the laminated material for packaging obtained by laminating the deposited film lacks transparency,
There is a problem that it is difficult to visually recognize the contents, and there is also a problem that the microwave oven lacks suitability. Next, in the barrier layer composed of the above polyvinylidene chloride-based resin, since it contains chlorine atoms, chlorine gas is generated when incinerated after use, which is not preferable for environmental hygiene. There is. In addition, the barrier layer composed of the ethylene-vinyl alcohol copolymer has the advantages of low oxygen permeability and low adsorptivity of flavor components. Therefore, the barrier layer composed of the ethylene-vinyl alcohol copolymer is shielded from water vapor, so that the laminated structure of the laminated material is complicated. As a result, there is a problem that the manufacturing cost is increased.

On one side of the plastic substrate,
In a transparent barrier film having a configuration in which a deposited film of an inorganic oxide such as silicon oxide and aluminum oxide is provided,
Compared with the conventional barrier material made of aluminum foil etc., it has excellent transparency, high barrier property against oxygen, water vapor, etc., and also excellent fragrance retention for contents, and furthermore, disposal There is no environmental problem at the time, and the demand for packaging materials is greatly expected. However, in the laminated material using the above-mentioned transparent barrier film, silicon oxide, a deposited film of an inorganic oxide such as aluminum oxide is inferior in flexibility, so that when the laminated material is rolled or bent. Cracks and the like are easily generated in a deposited film of an inorganic oxide. For example, cracks are easily generated in a post-processing process such as a printing process or a laminating process. When such a problem occurs, there is a problem that the barrier property is significantly reduced. 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 inorganic oxide deposited film, in this case, the inorganic oxide Increasing the thickness of the vapor-deposited film, on the other hand, tends to cause cracks and the like, and has the same problems as described above. Further, in the above-mentioned transparent barrier film, when the base film or the like constituting the transparent barrier film undergoes dimensional change due to absorption of moisture or the like, the deposited film of the inorganic oxide hardly follows the dimensional change, and the inorganic oxide Cracks and the like are easily generated in the deposited film of the object, and in this case, the same problem as described above occurs. In particular, when a polyamide-based resin film is used as the base film for vapor deposition, the polyamide-based resin film has a dimensional change due to moisture absorption of 2 or more, as compared with a generally used polyester-based resin film. About 10 times larger, so
The use of a polyamide-based resin film as the base film for vapor deposition means that, for example, during the formation of a vapor-deposited film of an inorganic oxide, the vapor-deposited film of the inorganic oxide follows the dimensional change of the polyamide-based resin film. Is extremely difficult, so it is virtually impossible.

[0005] In the above-mentioned transparent barrier film, 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 conversely,
If there is no barrier property, and if a silicon oxide vapor deposition film where X = 1, the barrier property is sufficient, but the film is colored brown and has no transparency at all. Usually, a deposited film of silicon oxide in the range of X = 1 to 2 is formed. However, when the film is colored yellow-brown and used as a barrier material, the appearance of the packaged product is poor. In addition, there is a problem that the 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, so that it can be used in post-processing such as printing and laminating. When a film or the like is bent, cracks or the like are easily generated in the deposited film, and there is a problem that the barrier property is remarkably reduced. Further, the deposited film of aluminum oxide is also made of AlO _x (X = 0 to 0) similarly to the above-described deposited film of silicon oxide.
1.5) formed of aluminum oxide represented by
When X is small, that is, when it is close to aluminum, the barrier properties are improved, the film is soft, and there is an advantage that the film is rich in flexibility. However, there is a problem that the film is colored brown. Because the ratio is large, the transparency is inferior, when used for packaging materials, etc., it becomes difficult to see the contents, and the microwave oven suitability is lost, and there is no difference from the conventional aluminum vapor deposition film It has problems. 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, the workability and the like are slightly inferior, but it is actually used with a focus on emphasizing its transparency. is there. Therefore, the present invention has been made in view of the above situation,
Even though a polyamide resin film is used as the base film for vapor deposition, it also has excellent transparency and high barrier properties, and has post-processing suitability, and in particular, has microwave oven suitability,
An object of the present invention is to provide a transparent barrier film suitable for packaging materials and the like and a laminated material using the same.

[0006]

As a result of various studies to solve the above problems, the present inventor has used a polyamide resin film as a base film for vapor deposition, and When an aluminum oxide deposited film is formed as a barrier layer on a base resin film, an aluminum oxide deposited film is formed on the surface of the polyamide resin film by a general formula AlO _x (where X is 1.0-1.
Represents a number in the range of 5. ), And the amorphous thin film of aluminum oxide is formed in the above-mentioned general formula in the depth direction from the film surface to the inner surface. A non-crystalline thin film of aluminum having a reduced value of is formed to produce a transparent barrier film, and then, for example, a heat-sealing resin layer, a base film layer Laminate etc. to produce a packaging laminate, and further produce a packaging container by making a bag or box using the packaging laminate,
Thereafter, when the packaging container was used and filled with various articles, the product had excellent transparency and high barrier properties. The crystalline thin film follows, and
Excellent adhesion between the polyamide-based resin film and the amorphous thin film of aluminum oxide, for example, without cracks during post-processing, has extremely high post-processing suitability, and furthermore, the packaging product is microwaved. Also, the present inventors have found that they have sufficient microwave oven suitability, and that they can produce a transparent barrier film having packaging suitability for various articles as a packaging material and the like and a laminate using the same can be produced. Things.

That is, the present invention comprises a polyamide-based resin film and a barrier layer provided on at least one surface of the polyamide-based resin film. Consisting of a thin film,
Further, the amorphous thin film of aluminum oxide may be a non-crystalline thin film of aluminum oxide represented by the general formula: AlO _x (where X represents a number in the range of 1.0 to 1.5). A transparent thin film comprising an amorphous thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the surface of the thin film to the inner surface. The present invention relates to a film and a laminated material using the film.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the transparent barrier film according to the present invention, the configuration of a laminated material and the like using the same will be described with reference to the drawings by exemplifying one or two, FIGS.
It is a schematic sectional view showing the layer composition of the transparent barrier film concerning the present invention, and Drawing 6-Drawing 8 show the layer composition of the laminated material manufactured using the above-mentioned transparent barrier film concerning the present invention. It is a schematic sectional drawing.

First, as shown in FIG. 1, a transparent barrier film A according to the present invention comprises a polyamide resin film 1 and a barrier layer 2 provided on at least one surface of the polyamide resin film 1. Is the basic structure. Thus, in the present invention, FIG.
As shown in FIG. 2, the barrier layer 2 shown in FIG. 2 is made of an amorphous thin film 2a of aluminum oxide. Further, as shown in FIG. 3, the amorphous thin film 2a of aluminum oxide shown in FIG. 2 has a general formula AlO _x (where X is a number in the range of 1.0 to 1.5). Represents.)
And a non-crystalline thin film 2b of aluminum oxide represented by Further, as shown in FIG. 4, the amorphous thin film 2b of aluminum oxide shown in FIG.
A non-crystalline thin film of aluminum oxide represented by the general formula AlO _X (where X represents a number in the range of 1.0 to 1.5), and the non-crystalline thin film of aluminum oxide Is a non-crystalline aluminum oxide thin film 2c in which the value of X decreases in the depth direction from the film surface to the inner surface. In addition, FIG.
In FIG. 4, reference numerals, A, 1, etc. in the figure have the same meaning as in FIG.

Next, another specific example of the transparent barrier film according to the present invention will be described. As shown in FIG. 5, as shown in FIG. 4, a general formula AlO _x shown in FIG.
Represents a number in the range of 1.0 to 1.5. ), The amorphous thin film of aluminum oxide in contact with the surface of the polyamide resin film 1 has at least a non-crystalline aluminum oxide film of the general formula AlO _x (where X is And a non-crystalline thin film 2d of aluminum oxide represented by the following formula:
Furthermore, on the above-mentioned amorphous thin film 2d of aluminum oxide, at least a general formula AlO _x (where
Represents a number in the range of 1.2 to 1.5. The transparent barrier film A1 having a configuration including at least two layers of the thin films 2d and 2e provided with the amorphous thin film 2e of aluminum oxide represented by the formula ( ₁₎ can be exemplified. The above examples illustrate one of the transparent barrier films according to the present invention, and are not limited thereto.For example, although not shown, as an amorphous thin film of aluminum oxide, polyamide The film may be provided not only on one surface but also on both surfaces of the resin film.

Next, in the present invention, a laminate manufactured using the above-mentioned transparent barrier film according to the present invention will be described by exemplifying one of the laminates. As the laminate according to the present invention, for example, As an example in which the transparent barrier film A shown in FIGS. 1 to 4 is used, as shown in FIG. 6, an amorphous thin film of aluminum oxide of the transparent barrier film A shown in FIGS. 2c (2, 2
Examples of the laminated material B include a configuration in which at least the heat-sealing resin layer 3 is laminated on the surfaces (a) and (2b). Further, as shown in FIG. 7, the laminated material according to the present invention has a configuration in which at least the base film layer 4 is laminated on the surface of the polyamide resin film 1 of the laminated material A shown in FIG. it can be exemplified laminate B _1. Furthermore, as the laminate according to the present invention, as shown in FIG. 8, the surface of the laminate B ₁ of the base film layer 4 as shown in Figure 7 above, further, at least, heat - tosyl - Le resin it can be exemplified laminate B ₂ having the structure obtained by laminating a layer 3a. 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 Layers, heat-sealing resin layers, etc., and further, by optionally laminating other base materials depending on the purpose of use, application, etc., it is possible to design and manufacture various forms of laminated materials. You can do it.

Next, in the present invention, an example of the structure of a packaging container formed by bag making or box making using the above-described laminated material will be described. For example, a description will be given by exemplifying a packaging container made from a bag or a box using the laminated material B shown in FIG. 6, as shown in a schematic perspective view of FIG. Are prepared, and the heatsink located at the innermost layer is prepared.
The surfaces of the conductive resin layers 3 and 3 are overlapped with each other, and thereafter, the three sides of the outer peripheral edge are heat sealed to seal.
The three-way seal type flexible packaging container C can be manufactured by forming the sealing parts 5, 5, 5 and providing the opening 6 above. Thus, in the present invention, although not shown, from the opening of the three-way seal type flexible packaging container manufactured above,
For example, filling contents such as food and drink, and others,
The upper opening portion is heat-sealed to form an upper sealing portion and the like, and further, if necessary, for example, subjected to a boil treatment, a retort treatment, etc., to form packaging products of various forms. It can be manufactured. In the present invention, it is needless to say that the present invention is not limited to the exemplary packaging container illustrated above, and the purpose, use, etc., may be a soft packaging bag, a liquid paper container, a paper can, It goes without saying that various other forms of packaging containers can be manufactured.

Next, in the present invention, the materials constituting the transparent barrier film, the laminated material and the like according to the present invention as described above, the manufacturing method and the like will be described. First, in the present invention, the transparent barrier according to the present invention is described. As the polyamide-based resin film constituting the conductive film, the laminated material, etc., any polyamide-based resin film that can hold an amorphous thin film of aluminum oxide can be used. For example, nylon 46, Nylon 6, nylon 6
6, nylon 610, nylon 612, nylon 11,
Various polyamide resin films or sheets such as nylon 12 and the like can be used. These polyamide-based resin films or sheets may be uniaxially or biaxially stretched, and have a thickness of about 10 to 200 μm, preferably about 10 to 200 μm.
About 100 μm is desirable. If necessary, the surface of the polyamide resin film or sheet may be subjected to a surface smoothing treatment by coating an anchor coating agent or the like on the surface.

Next, in the present invention, the amorphous thin film of aluminum oxide constituting the transparent barrier film, the laminate and the like according to the present invention is represented by a general formula AlO _x (where X is 0 0.5 to 1.5) can be used. Thus, in the present invention, the above general formula Al
As an amorphous thin film of aluminum oxide represented by O _x (where X represents a number from 0.5 to 1.5), a general formula AlO _x (where X is , 0.5-
Represents a number in the range of 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. A non-crystalline thin film of aluminum oxide can be used. In the above, as the value of X, basically, X = 0.5 or more can be used,
In the present invention, when X is less than 1.0, coloring is intense and transparency is inferior. Therefore, it is desirable to use one having X = 1.0 or more. Since aluminum and oxygen are completely oxidized, 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 1000 °.
It is desirable to arbitrarily select and form within the range of Å.

Next, in the present invention, a method for forming an amorphous thin film of aluminum oxide on a polyamide resin film will be described. Examples of the method include a vacuum deposition method, a sputtering method, and an ion plating method. Physical vapor deposition method (Physical)
Vapor Deposition method, PVD method),
Alternatively, a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method (Chemi
cal Vapor Deposition method, CVD
Method). In the present invention,
In the case of producing a transparent barrier film used as a packaging material, a vacuum deposition method is mainly used, and in part, a plasma enhanced chemical vapor deposition method is also used. To give a concrete example,
FIG. 10 is a schematic configuration diagram showing an example of a take-up type vacuum evaporation machine. As shown in FIG.
The polyamide resin film 1 unwound from the unwinding roll 12 passes through the coating drum 13 and
The crucible 15 enters the evaporation chamber 14 where the heated aluminum or aluminum oxide as an evaporation source is evaporated, and at this time, oxygen gas is ejected from the oxygen outlet 16. Meanwhile, a non-crystalline thin film of aluminum oxide is formed on the cooled polyamide-based resin film 1 on the coating drum 13 through the masks 17, 17, and then the non-crystalline thin film of aluminum oxide is formed. The transparent barrier film according to the present invention can be manufactured by winding the polyamide-based resin film 1 on which the conductive thin film has been formed onto a winding roll 18.

In the present invention, at least one surface of the polyamide resin film has the above-mentioned general formula Al
O _X (where in the formula, X represents. A number in the range of 1.0 to 1.5) a non-crystalline thin film of aluminum oxide which is represented by further non-crystalline oxide of aluminum A method for forming a non-crystalline thin film of aluminum oxide in which the value of X decreases in the depth direction from the film surface to the inner surface is specifically described as follows.
FIG. 11 is a schematic enlarged view of a part of the vacuum evaporator for forming a non-crystalline thin film of aluminum oxide using the take-up vacuum evaporator shown in FIG. . In the present invention, as shown in FIG. 11, first, an unwinding roll is placed in a vacuum chamber (not shown).
The polyamide-based resin film 1 drawn out from a tool (not shown) is fed into a deposition chamber 14 through a coating drum 13 in the direction of arrow P. Next, on the surface of the polyamide-based resin film 1 fed into the vapor deposition chamber 14 above, heated aluminum or an aluminum oxide as an evaporation source is evaporated in the crucible 15, and at this time, While ejecting oxygen gas from the oxygen outlet 16 and reacting both,
An amorphous thin film of aluminum oxide is formed through the masks 17 and 17. Therefore, in the present invention, when forming the amorphous thin film of aluminum oxide as described above, the crucible 15 and the oxygen
The crucible 15 and the oxygen outlet 16 are shifted from the center line i, and the crucible 15 is arranged at the position of the center line i. On the other hand, the oxygen outlet 16 is moved from the center line i to the polyamide. It is displaced on the discharge side of the base resin film 1. In the state of the above arrangement relationship, aluminum heated as the vapor source crucible 15, or aluminum oxide and evaporated, or aluminum, in a range surrounded by radiation H _1, oxides of aluminum Squirt. On the other hand, aluminum or
While ejecting the aluminum oxide, oxygen gas is further ejected from the oxygen outlet 16 into the area surrounded by the radiation H ₂ , and when the oxygen gas is ejected, the ejection concentration of the oxygen gas and the like are increased. , And lower oxygen at first, and then gradually increase oxygen to eject oxygen. As described above, aluminum or an oxide of aluminum and oxygen are applied to the surface of the polyamide-based resin film 1 while changing the oxygen gas ejection position or its concentration.
A gas of aluminum or an oxide of aluminum and an oxygen gas are ejected and evaporated through the masks 17 and 17.

Incidentally, as described above, aluminum,
Or, an aluminum oxide gas and an oxygen gas
When the film is ejected onto the surface of the polyamide-based resin film 1 and vapor-deposited, the aluminum or the aluminum oxide gas and the oxygen gas interact with each other when a vapor-deposited film is formed on the surface of the polyamide-based resin film 1. Acting first, film formation with low oxygen gas concentration, then
An amorphous thin film of aluminum oxide is formed on the surface of the polyamide-based resin film 1 through the masks 17 and 17 while the oxygen gas concentration is gradually increased, and as a result, the film proceeds from the film surface toward the inner surface. X above in the depth direction
Can form an amorphous thin film of aluminum oxide in which the value of (a) is reduced.

In the above, aluminum or an oxide of aluminum can also be used as a vapor deposition source, as well as a mixture of both. In the above description, the ejection of aluminum or an oxide of aluminum and oxygen gas is schematically illustrated as being radially spread and ejected by radiation H ₁ , radiation H _2, or the like. _1, only aluminum in the area of radiation H ₂ or,
It is presumed that the aluminum oxide gas and the oxygen gas do not exist but are actually ejected radially with a concentration distribution. Furthermore, in the above, the polyamide-based resin film advances in the direction of arrow P, and a non-crystalline thin film of aluminum oxide is formed in a region between the masks. Or, while spouting aluminum oxide, pass through a region with a low oxygen content, where
A thin film having a small X value of AlO _X is formed. Next, the polyamide-based resin film further proceeds, as the proportion of oxygen gradually increases, aluminum, or,
When aluminum oxide is ejected, a film having a large X value of AlO _X is formed. By the method as described above, an amorphous thin film of aluminum oxide is formed on the surface of the polyamide resin film, and the value of X decreases in the depth direction from the film surface toward the inner surface. It can form an amorphous 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, for example,
A method of moving a crucible or a coating drum, a method of tilting an oxygen outlet,
A non-crystalline thin film of aluminum oxide can be formed by various methods such as a method of vapor deposition by changing the gas concentration of oxygen from the oxygen blow-off port, and a method of connecting to a series or more.

[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 polyamide resin film is desirably about 10 to 800 m / min, preferably about 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. Thus, in the transparent barrier film according to the present invention, as described above, the general formula AlO _x (where X is 1.0
Represents a number in the range of ~ 1.5. ), The amorphous thin film of aluminum oxide in contact with the surface of the polyamide-based resin film is at least the general formula AlO _X (where X is 1.
Represents a number in the range of 0 to 1.2. ), Which is made of an amorphous thin film of aluminum oxide that follows the dimensional change of the polyamide-based resin film.
On the above-mentioned amorphous thin film of aluminum oxide, at least a general formula AlO _x (where X is 1.2
Represents a number in the range of ~ 1.5. At least two layers of thin film 2 provided with an amorphous thin film of aluminum oxide represented by
The transparent barrier film comprises d and 2e.

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 together 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, 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 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 may be 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, the film thickness, the degree of oxidation, and the distribution of the degree of oxidation are changed by changing the film transport speed, the amount of introduced oxygen, the position of the oxygen outlet, and the like. Was manufactured. In the above-mentioned transparent barrier film, the X value of aluminum oxide constituting the deposited film of aluminum oxide is reduced from X = 1.5 to X = 1.0 from the film surface in the depth direction. I made it.

Comparative Example 1 Using the vapor deposition machine of the above-mentioned Example 1, a thickness of 15 μm
Using the biaxially stretched nylon 6 film of the above, without changing the concentration of oxygen, in the same manner as in Example 1 above,
As a comparative example, a transparent barrier film having a 300-mm-thick aluminum oxide deposited film was manufactured. In the transparent barrier film described above, the X value of aluminum oxide constituting the deposited film of aluminum oxide is X =
It did not change at 1.0.

Comparative Example 2 Using the vapor deposition machine in the above-mentioned Example 1, a thickness of 15 μm
Using the biaxially stretched nylon 6 film of the above, without changing the concentration of oxygen, in the same manner as in Example 1 above,
As a comparative example, a transparent barrier film having a 300-mm-thick aluminum oxide deposited film was manufactured. In the transparent barrier film described above, the X value of aluminum oxide constituting the deposited film of aluminum oxide is X =
It was not changed 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 for 30 seconds in that state. 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 a method in which a non-stretched polypropylene film having a thickness of 20 μm is dry-laminated on a vapor-deposited film layer of a transparent barrier film via a two-component curing type urethane-based laminating adhesive layer. Producing the laminate according to the present invention, and then
The oxygen permeability and the moisture permeability of the laminated material were measured. (8). Suitable for microwave oven The transparent barrier film was placed in a microwave oven, and the state was observed. (9). Laminate strength This is to use the laminated material of (7) above,
m width and a tensile tester [A & D
(A & D), model name, Tensilon]. (10). Peeling Interface This was obtained by using the laminated material of (7) above, peeling it, and identifying and measuring the peeling interface with an electron microscope. The results of the above evaluation tests are shown in Table 1 below.

[0033]

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, Example 1 was excellent in oxygen permeability, moisture permeability, occurrence of cracks, suitability for post-processing, laminate strength, and the like, and also excellent in transparency and the like. Comparative Example 1 was inferior in coloring, transparency, suitability for microwave oven, laminating strength, etc.
In Comparative Example 2, the barrier property, generation of cracks,
It was inferior in post-processing suitability, laminate strength and the like.

Example 2 Deposition of the transparent barrier film produced in Example 1 above
Put a 5% solution of two-component curable polyester resin on the surface
It is used as an immersion agent and is coated to a film thickness of 1 μm.
Then, a low-density polyethylene is coated on the coating film surface.
Using a wrench, extrude it to a thickness of 60 μm and coat it.
To produce a laminated material according to the present invention having the following layer configuration.
did. 15 μm thick biaxially oriented nylon 6 film, thickness
Aluminum oxide deposited film of 300 mm / thickness of 1 μm
Primer agent layer / low-density polyethylene layer having a thickness of 60 μm.
Oxygen permeation manufactured by Mocon, USA
Degree measuring device [model name, OXTRAN]
As a result of measuring the oxygen permeability using, the oxygen permeability is
2.0cc / m ^Two-It was day. Also manufactured above
About the laminated material at 40 ° C. and 90% RH
Mocon company (MOCON company)
Species name, PERMATRAN]
As a result of measuring the water vapor transmission rate, the water vapor transmission rate was 2.
0 g / m^Two-It was day. The laminated material manufactured above
Used and made with a bag making machine to produce plastic bags
And filling the plastic bag with snacks.
When packaging products are manufactured by packaging,
However, no deterioration in the barrier properties was observed, and extremely good results were obtained.
I got a fruit.

[0036]

As is apparent from the above description, the present invention uses a polyamide resin film as a base film for vapor deposition, and thus forms a barrier layer on the polyamide resin film. When forming a deposited film of aluminum oxide, on the surface of the polyamide resin film,
The deposited film of aluminum oxide has a general formula AlO _x (wherein
X represents a number ranging from 1.0 to 1.5. ), And the amorphous thin film of aluminum oxide is formed in the above-mentioned general formula in the depth direction from the film surface to the inner surface. A non-crystalline thin film of aluminum having a reduced value of is formed to produce a transparent barrier film, and then, for example, a heat-sealing resin layer, a base film layer To produce a packaging laminate material, and further produce a packaging container by making a bag or a box using the packaging laminate material, and then use the packaging container, In addition, by filling and packaging various articles, it has excellent transparency and high barrier properties, furthermore, the amorphous thin film of aluminum oxide follows the dimensional change of the polyamide resin film, and Resin film and aluminum oxide Excellent close-adhesion with non-crystalline thin films, for example, no cracks during post-processing, extremely high post-processing suitability, and even if the packaged product is microwaved, it is sufficiently microwave-suitable Thus, a transparent barrier film having packaging suitability for various articles as a packaging material or the like and a laminated material using the same 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, the problems of opacity and deterioration of microwave oven suitability due to a small X value are eliminated by reducing the film thickness in a 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 rich in processability. In particular, cracks do not occur in post-processing such as printing and laminating, and as a result, deterioration of barrier properties and the like are not observed. This makes it possible to form a barrier film having extremely good post-processing suitability.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view showing a layer configuration of a transparent barrier film according to the present invention.

FIG. 3 is a schematic sectional view showing a layer configuration of a transparent barrier film according to the present invention.

FIG. 4 is a schematic sectional view showing a layer configuration of a transparent barrier film according to the present invention.

FIG. 5 is a schematic sectional view showing a layer configuration of a transparent barrier film according to the present invention.

FIG. 6 is a schematic 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. 7 is a schematic cross-sectional view showing a layer structure of a laminated material manufactured using the transparent barrier film according to the present invention.

FIG. 8 is a schematic cross-sectional view showing a layer structure of a laminated material manufactured using the transparent barrier film according to the present invention.

FIG. 9 is a schematic 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 schematic configuration diagram illustrating an example of a take-up type vacuum evaporation machine.

11 is a schematic enlarged view of a part of the vacuum evaporation machine for forming a non-crystalline thin film of aluminum oxide using the winding vacuum evaporation machine shown in FIG. 11;

[Explanation of symbols]

A Transparent barrier film A ₁ Transparent barrier film 1 Polyamide resin film 2 Barrier layer 2 a Non-crystalline thin film of aluminum oxide 2b General formula AlO _X (where X is 1.0 to
Represents a number in the range of 1.5. Noncrystalline thin film 2c formula AlO _X of aluminum oxide (but represented by), wherein, X is 1.0
Represents a number in the range of 1.5. ), Wherein the value of X decreases in the depth direction from the surface to the inner surface of the amorphous thin film of aluminum oxide. Non-crystalline thin film of aluminum 2d General formula AlO _X (where X is 1.0 to 1.0)
Represents a number in the range of 1.2. 2e, a non-crystalline thin film of aluminum oxide represented by the following general formula: AlO _x (where X is 1.2 to
Represents a number in the range of 1.5. 3) Heat-sealing resin layer 3a Heat-sealing resin layer 4 Base film layer 5 Seal part 6 Opening B Laminate C Three-way sheet -Roll type flexible packaging container

Continued on front page F-term (reference) 4F100 AA19B AK01C AK01E AK46A AT00D BA02 BA03 BA04 BA05 BA06 BA10A BA10C BA10D BA10E BA13 BA44 EJ38A GB15 JA12B JD02B JD03 JD04 JL01 JL12C JL12E JM02B JN01 Y

Claims (7)

[Claims] 1. A polyamide resin film, comprising a barrier layer provided on at least one surface of the polyamide resin film, further comprising a non-crystalline thin film of aluminum oxide, Furthermore, the amorphous thin film of the aluminum oxide has a general formula of AlO _x (where,
In the formula, X represents a number in the range of 1.0 to 1.5. A) an amorphous thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the surface of the thin film toward the inner surface. A transparent barrier film comprising: 2. The transparent barrier film according to claim 1, wherein the polyamide resin film comprises a biaxially stretched nylon film. 3. A non-crystalline thin film of aluminum oxide,
The transparent barrier film according to claim 1, wherein the film has a thickness of 60 ° to 1000 °. 4. An amorphous thin film of aluminum oxide in contact with a surface of a polyamide resin film,
General formula AlO _X (where X is 1.0 to 1.2)
Represents the number of ranges. 2. The method according to claim 1, wherein the film comprises an amorphous thin film of aluminum oxide represented by the following formula:
4. The transparent barrier film described in any one of items 1 to 3. 5. A polyamide resin film, comprising a barrier layer provided on at least one surface of the polyamide resin film, further comprising a non-crystalline aluminum oxide thin film, Furthermore, the amorphous thin film of the aluminum oxide has a general formula of AlO _x (where,
In the formula, X represents a number in the range of 1.0 to 1.5. A) an amorphous thin film of aluminum oxide, wherein the value of X decreases in the depth direction from the surface of the thin film toward the inner surface. A laminate comprising at least a heat-sealing resin layer laminated on a surface of a barrier layer of a transparent barrier film comprising: 6. The laminated material according to claim 5, wherein a base film layer is further laminated on the non-barrier layer side of the transparent barrier film. 7. The method according to claim 5, wherein a base film layer and a heat-sealing resin layer are further laminated on the non-barrier layer side of the transparent barrier film. Laminated material.