JPH10249989A - Transparent barrier film, laminate material using the same, and packing container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance close adhesiveness, transparency, barrier properties and moisture permeability resistance by providing a barrier layer of a membrane of inorg. oxide to one surface of a coextrusion multilayered sealant film based on a polypropylene resin. SOLUTION: A polypropylene resin and a heat-sealable resin are co-extruded to form a co-extrusion multilayered sealant film 3 based on a polypropylene resin consisting of a polypropylene resin layer 1 and a heat-sealable resin layer 2. A barrier layer 4 composed of a membrane of inorg. oxide is provided on the surface of the polypropylene resin layer 1. As the polypropylene resin, a propylene homopolymer or copolymer is used and the thickness thereof is set to about 5-100μm. The thickness of the heat-sealable resin layer 2 is set to about 5-200μm and the thickness of the multilayered sealant film 3 is set to about 10-300μm. The membrane 4 of inorg. oxide is formed by making oxide of metal amorphous and the thickness thereof is set to 50-3000Å.

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 which is excellent in transparency, barrier properties against water vapor or oxygen, impact resistance, and the like. Food packaging, pharmaceutical packaging, detergents, shampoos, oils, non-food fields such as toothpaste, electronic parts packaging field, etc. 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 films have been developed as packaging materials satisfying barrier properties against oxygen, water vapor, etc., or moisture resistance in packaging of articles such as foods, pharmaceuticals, and electronic parts. Proposed. For example, (1). Polyvinylidene chloride resin film, vinylidene chloride-based copolymerizable monomer, such as vinyl chloride, methyl methacrylate, acrylonitrile, or other copolymer film, or polyvinylidene chloride A polyvinylidene chloride-based resin coat film in which a composition containing a resin is coated on the surface of a plastic film such as polypropylene, polyester or polyamide; (2). A polyvinyl alcohol film or an ethylene-vinyl alcohol copolymer film; (3). An aluminum foil, a vapor-deposited film in which aluminum is vapor-deposited on the surface of a plastic film, and the like are known. However, in the barrier film as described above, for example, the above (1)
Is unsuitable for packaging laminates that require a high degree of gas barrier properties, and has the problem that harmful gases such as chlorine gas are generated during incineration of waste treatment. (2) is inferior in moisture permeation resistance, in particular, has a problem that the oxygen barrier property is dependent on humidity, and (3) is inferior in transparency.
Contents cannot be confirmed, heating by microwave oven is not possible, and furthermore, it is difficult to collect and reuse in disposal, and at the time of incineration, aluminum remains as slag, damaging incinerators, etc. There is also the problem of doing so. Therefore, for a barrier film as described above, 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 on a flexible plastic substrate, and the transparent barrier film was used. Laminates for packaging have been proposed. This is excellent in transparency as compared with a conventional barrier film and a laminated material for packaging using the same, and has a high barrier property against water vapor, oxygen, etc. Further, there is no environmental problem at the time of disposal, and the demand for packaging materials and the like is greatly expected.

[0003]

However, in the above-mentioned transparent barrier film, the adhesion between the flexible plastic substrate and the inorganic oxide vapor-deposited film is weak, and the gas barrier property is not sufficient. There is a point. In order to improve the adhesion between the flexible plastic substrate and the deposited film of the inorganic oxide, for example, a resin composition containing an isocyanate compound or the like is coated on the surface of the flexible plastic substrate.
Although a pretreatment method for coating is proposed, the coating film has a rough surface and its material is soft, so that the growth of the deposited film does not work well.
There is a problem that the degree of vacuum is reduced during the deposition due to the residual solvent contained in the film, and it is difficult to form a desired deposited film. In addition, the above-mentioned transparent barrier film, the barrier performance in packaging laminates and the like using the same, compared to the original barrier material such as aluminum foil,
There is a problem that the barrier performance against oxygen, water vapor and the like is inferior. Further, in the above-mentioned transparent barrier film, a packaging laminate using the same, and the like, an attempt has been made to increase the thickness of a vapor-deposited film in order to increase the barrier performance. However, a transparent barrier film as described above,
Also, in a packaging laminate using the same, the barrier layer itself composed of a vapor-deposited film of an inorganic oxide is inferior in flexibility, so that when the film is rolled or folded, the vapor-deposited film is easily cracked. For example, when the above-mentioned operation is employed during post-processing such as printing and laminating, cracks are easily generated, and once cracks occur, the barrier property is significantly reduced. There is. Further, in the above-mentioned transparent barrier film, and in a packaging laminate and the like using the same, for example, in order to improve the barrier properties, when trying to increase the thickness of the vapor deposition film, conversely, the vapor deposition film By increasing the film thickness, cracks and the like are more likely to occur, and have the same problems as described above. Further, in the above-mentioned transparent barrier film, and in a packaging laminate using the same, when this causes a dimensional change or the like due to moisture absorption, the deposited film is difficult to follow the dimensional change, and cracks are easily generated. Also have the same problems as described above. In addition, when the above film thickness is improved, the deposited film is colored, and, for example, when used as a packaging material, there is a problem that the commercial value of the contents is impaired. Accordingly, the present invention has been made in view of the above circumstances, and has improved adhesion between a flexible plastic substrate and a deposited film of an inorganic oxide, and has excellent transparency and high barrier properties. An object of the present invention is to provide a transparent barrier film which is rich in moisture permeability, has good post-processing suitability, and has good storage suitability, and a laminated material and a packaging container using the same.

[0004]

As a result of various studies to solve the above problems, the present inventor focused on a co-extruded multilayer sealant film based on a polypropylene resin. On one surface of the transparent barrier film, a barrier layer made of a thin film of inorganic oxide is provided to produce a transparent barrier film. Thus, at least a substrate is formed on the barrier layer made of a thin film of inorganic oxide of the transparent barrier film. When a laminated material is manufactured by laminating the material film layers, a packaging container is manufactured by bag making or box making using the laminated material, and various articles are filled and packaged in the packaging container. , Excellent adhesion between a flexible plastic substrate and a thin film such as a vapor-deposited film of an inorganic oxide, and has excellent transparency and high barrier properties; furthermore, excellent moisture permeability, excellent storage suitability, etc. In addition, there is no crack during post-processing, A transparent barrier film having high post-processing suitability, and even having sufficient microwave oven suitability even when the packaged product is subjected to microwave oven, and having packaging suitability for various articles as a packaging material, and a laminate using the same. The present invention has been completed by finding that materials and packaging containers can be manufactured.

That is, the present invention provides a transparent barrier, wherein a barrier layer comprising a thin film of an inorganic oxide is provided on one surface of a co-extruded multilayer sealant film based on a polypropylene resin. The present invention relates to a film, a laminated material using the film, and a packaging container.

[0006]

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

The transparent barrier film A according to the present invention comprises:
As shown in FIG. 1, polypropylene resin and heat
Co-extruded multilayer sheet based on a polypropylene-based resin composed of a polypropylene-based resin layer 1 and a hermetic resin layer 2 using
The multi-layer sealant film 3 is manufactured, and a barrier layer 4 made of a thin film of an inorganic oxide is provided on one surface of the co-extruded multilayer sealant film 3. In the above, although not shown, the barrier layer composed of a thin film of an inorganic oxide can be provided on one or both surfaces of the co-extruded multilayer sealant film. It is desirable to provide on the surface of the polypropylene-based resin layer constituting the runt film. That is, in the present invention, by providing a barrier layer composed of a thin film of an inorganic oxide on the surface of the polypropylene-based resin layer constituting the co-extruded multilayer sealant film,
For example, a laminate comprising a biaxially oriented polyethylene terephthalate film / a barrier layer comprising an inorganic oxide thin film / adhesive layer / a non-oriented polypropylene resin layer;
Compared with a conventional laminated material such as an axially stretched polyethylene terephthalate film / a barrier layer composed of a thin film of an inorganic oxide / adhesive layer / a linear low-density polyethylene resin layer, for example, an adhesive layer, etc. This has the advantage of being able to reduce the number of layers in the layer configuration described above, and has the effect of reducing costs and the like. Thus, the above-described example is an example of the transparent barrier film according to the present invention, and the present invention is not limited thereto. May be formed by laminating not only one thin film but also two or more layers, and the inorganic oxide thin film may be formed of not only one kind but also two or more kinds of inorganic oxides. .

Next, a laminate manufactured using the transparent barrier film according to the present invention will be described with reference to a few examples. As the laminate according to the present invention, for example, as shown in FIG. A laminated material B obtained by laminating at least the base film layer 5 on the surface of the barrier layer 4 made of the inorganic oxide thin film of the transparent barrier film A shown in FIG. Further, as shown in FIG. 3, the laminated material according to the present invention further includes a heat-sealing resin layer 2a on the base material film layer of the laminated material B shown in FIG. Can be listed. 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, heat-sealing resin layer, etc.
It is possible to design and manufacture various forms of laminated materials by arbitrarily laminating other base materials. In the present invention, the base film layer, the heat-sealing resin layer, the lamination position of the other layers, depending on the purpose of use, use, etc.,
By laminating at any position, various forms of laminated materials can be designed and manufactured.

Next, in the present invention, the structure of the packaging container according to the present invention, which is formed by using the above-mentioned laminated material to form a bag or a box, will be described. By way of example, a description will be given of a packaging container made from a bag or a box using the laminated material B shown in FIG. 2 above. As shown in a perspective view of FIG. 4, two laminated materials B and B are prepared. Then, the heat-sealing resin layers 2, 2 positioned at the innermost layer are superposed on each other with the surfaces thereof facing each other, and then the three sides of the outer peripheral edge are heat-sealed to form a seal portion. 6,
By forming 6 and 6, the three-way seal type flexible packaging container D according to the present invention can be manufactured.

Next, as a packaging container according to the present invention, as shown in the plan view of FIG.
First, a predetermined crease l is used.
(Indicated 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 the perspective view of FIG. The attachment portion 7 is overlapped with the other side end portion 9 (shown in FIG. 5), 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 a packaging container according to the present invention, as shown in the plan view of FIG.
First, a blank plate 8a for forming a rectangular paper container having a sticking portion 7a and the like, and capable of forming a cylindrical body portion is punched out from the laminated material C, and then manufactured. FIG.
As shown in the perspective view of FIG.
Is overlapped with the other side end 9a (shown in FIG. 7), and the overlapped portion is heat-sealed to form a side end seal 10a to produce a cylindrical body 11a. The cylindrical body 11a
For example, a bottom plate 14 having a cylindrical shape is
Forming a bottom seal portion 15 to form a bottom portion 14a;
Furthermore, an upper seal portion 19 is formed on the upper portion of the cylindrical container 11a by, for example, heat-sealing a cylindrical lid plate 18 having a drinking mouth 17 sealed with a peeling piece 16. Thus, the lid 18a can be configured to manufacture the cylindrical paper can-shaped packaging container F according to the present invention. In the present invention, it is needless to say that the present invention is not limited to the exemplary packaging container illustrated above,
It goes without saying that various forms of packaging containers can be manufactured depending on the purpose, application, and the like.

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 the polypropylene resin constituting the polypropylene resin layer of the co-extruded multilayer sealant film, heat resistance, transparency, etc. , A polypropylene-based resin rich in water content can be used. Specifically, as the above-mentioned polypropylene-based resin, a homopolymer or co-polymer of propylene, or a blend of these with other resins can be used. Thus, in the present invention, when co-extruded using the above-mentioned polypropylene resin, it has excellent flatness and non-stretching which is rich in adhesion to a barrier layer composed of a thin film of inorganic oxide. It is desirable to form a polypropylene resin layer. In the present invention, the thickness of the polypropylene resin layer of the co-extruded multilayer sealant film is about 5 to 100 μm, preferably 10 to 50 μm.
The m-th position is desirable.

Next, in the present invention, among the materials constituting the transparent barrier film according to the present invention, the heat sealability constituting the heat sealable resin layer of the co-extruded multilayer sealant film is provided. As the resin, a resin having a relatively lower heat resistance temperature than the above-mentioned polypropylene-based resin, and a resin that can be melted and fused together by heat 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,
Acid-modified polyolefin obtained by modifying a polyolefin resin such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Resins such as resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, and others can be used. In the present invention, the thickness of the heat-sealing resin layer is preferably about 5 μm to 200 μm, more preferably about 10 μm to 100 μm.

Next, in the present invention, a co-extruded multilayer sealant film will be described. In the present invention, the above-mentioned polypropylene resin and heat-sealing resin are used as resin materials for extrusion. For example,
The co-extruded multilayer sealant film according to the present invention can be manufactured by forming a film using a film forming method such as a T-die co-extrusion method and a co-extrusion inflation method.
In the present invention, the thickness of the co-extruded multilayer sealant film is about 10 μm to 300 μm, preferably about 20 μm to 100 μm, and within this range, the polypropylene resin constituting the co-extruded multilayer sealant film It is desirable to adjust each thickness of the layer and the heat-sealing resin layer.

Next, in the present invention, the thin film barrier layer of inorganic oxide constituting the transparent barrier film will be described. The thin film of inorganic oxide constituting such a barrier layer is basically a metal oxide. Any amorphous thin film can be used. For example, silicon (Si), aluminum (Al), magnesium (M
g), calcium (Ca), potassium (K), tin (S
n), sodium (Na), boron (B), titanium (T
A thin film in which an oxide of a metal such as i), lead (Pb), zirconium (Zr), yttrium (Y), or the like is made amorphous can be used. Thus, as a material suitable for a packaging material or the like, an oxide of a metal such as silicon (Si) or aluminum (Al) may be used.
Can be mentioned. Thus, a thin film obtained by converting the above metal oxide into an amorphous state can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. For example, it is represented by MO _X (where M represents a metal element, and the value of X varies depending on the metal element), such as SiO _X , AlO _X , and MgO _X. The range of the value of X is 0 to 2 for silicon (Si) and 0 to 2 for aluminum (Al).
1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0, potassium (K) is 0-0.5,
Tin (Sn) is 0-2, and sodium (Na) is 0-2.
0.5, boron (B) is 0-1,5, titanium (Ti)
Is 0-2, lead (Pb) is 0-1, zirconium (Z
r) can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 1.5. In the above, when X = 0, it is a perfect metal, it is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention, as the packaging material, generally, except for silicon (Si) and aluminum (Al),
Poorly used examples, silicon (Si) is 1.0 to
As for 2.0 and aluminum (Al), those having a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the inorganic oxide thin film as described above varies depending on the type of metal or metal oxide to be used.
It is desirable to select and form arbitrarily in the range of about 0 to 1000 °. In the present invention, the inorganic oxide thin film is not limited to one layer of the inorganic oxide thin film,
It may be in the form of a laminate in which two or more layers are laminated, and the metal or metal oxide to be used is an inorganic oxide which is used in one kind or a mixture of two or more kinds and mixed with different materials May be formed.

Next, a method for forming a thin film of an inorganic oxide in the present invention will be described. Examples of such a method include a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion plating method.
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,
When a transparent barrier film used for a packaging material is produced, mainly a vacuum deposition method is used, and in part, a plasma enhanced chemical vapor deposition method is also used. As a specific example, FIG. 9 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine. As shown in FIG. 10, a co-extruded multilayer sealant film 113 fed from an unwinding roll 112 in a vacuum chamber 111 is coated with a coating drum 11.
4 and into the deposition chamber-115, where:
The co-extruded multilayer sealant film 113 on the cooled coating drum 114 is evaporated while evaporating the evaporation source heated in the crucible 116 and, if necessary, discharging oxygen or the like from the oxygen outlet 117. A vapor-deposited inorganic oxide film is formed thereon via masks 118, 118, and then the co-extruded multilayer sealant film 113 on which the vapor-deposited film is formed is fed into a vacuum chamber 111 to take up a roll 119. By winding the film, a thin film of the inorganic oxide according to the present invention can be formed.

Further, in the present invention, a method of forming a thin film of an inorganic oxide will be specifically described. The above-mentioned metal oxide is used as a raw material, which is heated to form a co-extruded multilayer sealant film. Vacuum evaporation method of vapor deposition on one side, or oxidation reaction vapor deposition method of using a metal or metal oxide as a raw material, introducing oxygen and oxidizing it, and vapor-depositing on one side of a co-extruded multilayer sealant film Further, a vapor-deposited film can be formed by using a plasma-assisted oxidation reaction vapor deposition method in which an oxidation reaction is promoted by plasma. In addition,
In the present invention, when forming a deposited film of silicon oxide, the deposited film can be formed by a plasma chemical vapor deposition method using organosiloxane as a raw material. Also,
In the above, in order to enhance the adhesion of the deposited film, the surface of the co-extruded multilayer sealant film is subjected to a surface treatment such as a corona discharge treatment, a frame treatment, and a coating treatment with an anchor coating agent. Can be arbitrarily performed in advance.

Further, in the present invention, the base film constituting the base film layer is, for example, a basic material when forming a packaging container.
Has excellent properties in physical, chemical, other, etc.
In particular, a resin film or sheet having strength, toughness, and heat resistance can be used, and specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, and a polyolefin. Films or sheets of a tough resin such as a base resin, a polycarbonate resin, a polystyrene resin, a polyacetal resin, a fluorine resin, and others 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 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 base film constituting the base film layer, for example, various paper base materials constituting the paper layer can be used. In the present invention, the paper substrate is provided with moldability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper substrate, or pure white roll paper,
Paper base materials such as kraft paper, paperboard, and 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, the heat-sealing resin constituting the heat-sealing resin layer formed on the base film layer is melted by heat and fused to each other. A resin film or sheet that can be used can be used, and 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,
Acid-modified polyolefin obtained by modifying a polyolefin resin such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Resins, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, and other resin films or sheets 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 preferably about 5 μm to 300 μm, and more preferably about 10 μm to 100 μm.

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 High-density polyethylene, polypropylene, ethylene-propylene copolymer or other resin film or sheet, or saponified polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer having a barrier property against oxygen, water vapor, etc. Films or sheets of various colored resins having a light-shielding property obtained by adding a colorant such as a pigment to the resin and other desired additives and kneading to form a film. 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 is usually about 5 μm to 300 μm,
Further, the thickness is 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 such a method, a method of laminating when manufacturing a normal packaging material is described. For example, wet laminating
Method, dry lamination method, solvent-free dry lamination method, extrusion lamination method, T-die extrusion molding method, co-extrusion lamination method, inflation method, co-extrusion inflation method, etc. It can be carried out. Thus, in the present invention, when performing the above lamination, if necessary, for example, corona treatment,
The film can be subjected to a pretreatment such as an ozone treatment. For example, an anchor coating agent such as an isocyanate (urethane), a polyethyleneimine, a polybutadiene, or an organic titanium, or a polyurethane, Use of known pretreatments such as laminating adhesives such as polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., anchor coating agents, adhesives, etc. Can be.

Next, in the present invention, a method of making a bag or a box using the above-described 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 a laminated material manufactured by such a method, the heat-sealing resin layer of the inner layer is made to face the surface, and it is folded or the two sheets are overlapped, and furthermore, the peripheral edge portion is formed. A bag can be formed by providing a seal portion by heat sealing. Thus, as the bag making method, the above-mentioned laminated material is folded with its inner layer facing the surface, or two of them are overlapped,
Further, the peripheral end portion of the outer periphery is formed, for example, by a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket-attached seal type ( According to the present invention, a heat seal is formed according to a heat seal form such as a (pyrro-seale type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. Various forms of packaging containers can be manufactured. Others, for example, self-supporting packaging bags (standing pouches)
And the like can be manufactured, and in the present invention, a tube container and the like can be manufactured using the above-mentioned laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal,
Can be performed by a known method such as 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 a 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 beverages, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other articles. It is used for filling and packaging.

[0027]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 Using a heat-resistant polypropylene resin and a low-density polyethylene resin, a T-die co-extrusion method was used to produce a 40 μm-thick co-extruded multilayer sheet film. In the above co-extruded multilayer sheet film,
The thickness of the polypropylene resin layer was 25 μm, and the thickness of the low density polyethylene resin layer was 15 μm.
Next, on the surface of the polypropylene resin layer of the co-extruded multilayer sheet film manufactured as described above, a 200-mm-thick silicon oxide vapor-deposited film is formed by using a plasma CVD method to form a transparent barrier film according to the present invention. Manufactured. Next, about the transparent barrier film produced above, at 23 ° C., 9
Under the condition of 0% RH, an oxygen permeability measuring device [model name, Oxtran (OXT) manufactured by MOCON, USA]
RAN 2/20)] was used to measure oxygen permeability. Further, the transparent barrier film produced above was subjected to a moisture permeability measuring device (model name, part number) manufactured by MOCON, USA under the conditions of 37.8 ° C. and 100% RH.
Water vapor permeability was measured using PERMATRAN 3/31). Regarding the above measurement results,
The oxygen permeability was 1.2 cc / m ² · day, and the water vapor permeability was 1.2 g / m ² · day.

Example 2 On one side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a polyurethane two-part curable adhesive was
g / m ² (dry state), and then the transparent barrier film manufactured in Example 1 is bonded to the coated surface with the silicon oxide deposited film surface facing the transparent barrier film. Was. After an aging treatment for 3 days, a laminated material according to the present invention having the following layer constitution was produced. Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm / adhesive layer / evaporated film of silicon oxide having a thickness of 200 ° / coextruded multilayer sealant film having a thickness of 40 μm. ℃, 90%
Under the conditions of RH, an oxygen permeability measuring device [model name, OXTRA (OXTRA) manufactured by MOCON, USA]
N 2/20)] was used to measure oxygen permeability. Moreover, about 37.8 degreeC and 10 degree about the laminated material manufactured above.
Under a condition of 0% RH, a moisture permeability measuring device [model name, Permatran (PERMA) manufactured by MOCON, USA
TRAN 3/31)]. For the above measurement results, the oxygen permeability was 0.7
cc / m ² · day, and the water vapor permeability is
It was 1.0 g / m ² · day. Next, two sheets of the laminated material manufactured as described above are used, and the heat-sealing resin layers of the co-extruded multilayer sealant film are superimposed on each other. A three-way seal-type plastic bag was manufactured by the manufacturing machine. Next, the plastic bag prepared above was filled with potato chips through the opening, and then the opening was heat-sealed to produce a packaged product. No deterioration was observed, and very good results were obtained.

Example 3 One side of a paper having a basis weight of 200 g / m ² was extruded to a thickness of 30 μm using low-density polyethylene, and then laminated.
On the other surface of the paper, the transparent barrier film produced in Example 1 was used, and the silicon oxide vapor-deposited film surface was opposed to the transparent barrier film.
m and extruded to obtain a laminated material according to the present invention having the following layer constitution. Low-density polyethylene layer having a thickness of 30 μm / basis weight 200 g /
coextrusion of low density polyethylene layer / thickness of 200Å deposited film-thickness 40μm of silicon oxide paper / thickness 30μm of the m ² multilayer sheet - Holland Film Next, the laminate produced above, 23 ° C., 90 %
Under the conditions of RH, an oxygen permeability measuring device [model name, OXTRA (OXTRA) manufactured by MOCON, USA]
N 2/20)] was used to measure oxygen permeability. Moreover, about 37.8 degreeC and 10 degree about the laminated material manufactured above.
Under a condition of 0% RH, a moisture permeability measuring device [model name, Permatran (PERMA) manufactured by MOCON, USA
TRAN 3/31)]. For the above measurement results, the oxygen permeability was 1.5
cc / m ² · day, and the water vapor permeability is
It was 0.3 g / m ² · day. Next, using the laminated material manufactured as described above, first, a blank plate for forming a paper container is manufactured from the laminated material, and then, using the blank plate, the ends thereof are overlapped with each other to form a polymerized edge. The portion was heat-welded to produce a square body for forming a paper container. Thereafter, one opening of the square body was folded and heat-sealed to form a bottom, thereby manufacturing a paper container. Next, the contents are filled from the upper opening of the paper container, and then the opening is folded and heat-sealed to form a roof-type upper seal, thereby producing a packaged product. did. The above packaged products have high barrier properties and have shown good results.

Comparative Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was coated on one side with a thickness of 20 μm by plasma CVD.
A transparent barrier film was manufactured by forming a 0 ° silicon oxide deposited film. On the other hand, a polyurethane-based two-component curable adhesive is applied on one side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm at a rate of 3 g / m ² (dry state), and then the above-mentioned coated surface is applied. Then, the transparent barrier film produced above is bonded with the silicon oxide vapor-deposited film surface facing thereto, and a polyurethane-based polyethylene terephthalate film having a thickness of 12 μm is coated on the transparent barrier film with a polyurethane-based film. 3g of two-part curable adhesive
/ M ² (dry state), and thereafter, a 60 μm-thick unstretched polypropylene film is bonded to the above-mentioned coated surface, and then subjected to an aging treatment for 3 days.
A laminated material having the following layer configuration was manufactured. Non-stretched biaxially oriented polyethylene terephthalate film having a thickness of 12 μm / adhesive layer / vapor-deposited silicon oxide film having a thickness of 200 ° / biaxially stretched polyethylene terephthalate film having a thickness of 12 μm / adhesive layer / thickness of 60 μm Polypropylene film Next, about the laminated material manufactured above, 23 degreeC, 90%
Under the conditions of RH, an oxygen permeability measuring device [model name, OXTRA (OXTRA) manufactured by MOCON, USA]
N 2/20)] was used to measure oxygen permeability. Moreover, about 37.8 degreeC and 10 degree about the laminated material manufactured above.
Under a condition of 0% RH, a moisture permeability measuring device [model name, Permatran (PERMA) manufactured by MOCON, USA
TRAN 3/31)]. For the above measurement results, the oxygen permeability is 0.8
cc / m ² · day, and the water vapor permeability is
1.2 g / m ² · day, which was slightly inferior to the laminate of Example 2 according to the present invention.

[0031]

As apparent from the above description, the present invention focuses on a co-extruded multilayer sealant film based on a polypropylene-based resin, and on one side thereof, a thin film of an inorganic oxide. A transparent barrier film is manufactured by providing a barrier layer consisting of: and a laminated material is manufactured by laminating at least a base film layer on a barrier layer made of a thin film of an inorganic oxide of the transparent barrier film. And, further, using the laminated material to make a bag or box to produce a packaging container,
Various kinds of articles are filled and packed in the packaging container to have excellent adhesion between the flexible plastic substrate and a thin film such as a vapor-deposited film of inorganic oxide, and have excellent transparency and high barrier properties. And
Furthermore, it has excellent moisture permeability, storage suitability, etc., furthermore, it has no post-processing cracks, etc. and has extremely high post-processing suitability. A transparent barrier film having packaging suitability for various articles as a packaging material, a laminated material and a packaging container using the same can be produced.

[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 showing a layer structure of a laminated material manufactured using the transparent barrier film according to the present invention.

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

FIG. 4 is a perspective view showing a configuration of a packaging container made from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 5 is a plan view showing the configuration of a packaging container formed from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 6 is a perspective view showing a configuration of a packaging container formed from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 7 is a plan view showing a configuration of a packaging container made from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 8 is a perspective view showing a configuration of a packaging container made from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 9 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polypropylene resin layer 2 Heat-sealing resin layer 2a Heat-sealing resin layer 3 Co-extrusion multilayer sealant film 4 Barrier layer consisting of a thin film of indefinite oxide 5 Base film layer 6 Seal Part 7 Adhesion part 8 Blank plate for forming paper container 9 Side end 10 Side end seal part 11 Body 12 Bottom 13 Roof type seal part 7a Adhesion part 8a Blank plate 9a for forming paper container 9a side End 10a Side end seal 11a Cylindrical trunk 14 Cylindrical bottom plate 14a Bottom 15 Bottom seal 16 Peeling piece 17 Drinking port 18 Cylindrical lid 18a Lid 19 Upper seal 111 Vacuum chamber 112 Unwinding roll 113 Co-extruded multilayer sealant film 114 Coating drum 115 Deposition chamber 116 Crucible 117 Oxygen outlet 118 Mask 119 Roll Take B - Le A transparent barrier film B laminated material C laminate D Mikatashi - le type flexible packaging container E roof type paper packaging container F cylindrical paper can-shaped packaging containers l Orikei

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C23C 16/40 C23C 16/40 // C08J 7/04 CES C08J 7/04 CESP

Claims (7)

[Claims] 1. A transparent barrier film characterized in that a barrier layer made of a thin film of an inorganic oxide is provided on one surface of a co-extruded multilayer sealant film based on a polypropylene resin. 2. The transparent barrier film according to claim 1, wherein a barrier layer comprising a thin film of an inorganic oxide is provided on the polypropylene resin layer surface of the co-extruded multilayer sealant film. 3. A transparent barrier film comprising a barrier layer made of an inorganic oxide thin film provided on one side of a co-extruded multilayer sealant film based on a polypropylene-based resin. And a base material provided with a base film layer. 4. The laminate according to claim 3, wherein the co-extruded multilayer sealant film is a transparent barrier film in which a barrier layer made of a thin film of an inorganic oxide is provided on the polypropylene resin layer surface. Wood. 5. A heat-sealing resin layer is further provided on a substrate film layer.
Or the laminated material described in 4. 6. A transparent barrier film comprising a barrier layer made of a thin inorganic oxide film on one side of a co-extruded multilayer sealant film based on a polypropylene-based resin. A packaging container characterized by using a laminated material provided with a base material film layer, and making this into a bag or a box. 7. The package according to claim 6, wherein the co-extruded multilayer sealant film is a transparent barrier film in which a barrier layer made of a thin film of an inorganic oxide is provided on the surface of the polypropylene resin layer. Container.