JPH10193502A - Transparent barrier film, laminated material and packaging container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance an adhesion of a material and a deposited film and to realize an article having an excellent transparency, a high barrier properties and a post process suitability by providing a plasma treated surface at least on one surface of a flexible plastic base material, and providing a thin film of an inorganic oxide with the plasma treated surface. SOLUTION: A transparent barrier film A used for a laminated material and a packaging container is formed by providing a plasma treated surface 2 at least on one surface of a flexible plastic base material 1, further, providing an inorganic oxide thin film 3 on the plasma treatment surface 2. The plasma treatment surface 2 is formed by using a plasma surface treatment method performing surface modification by using a plasma gas generated by ionizing a gas by an electrical arc discharge to enhance an adhesion of the flexible plastic base material 1 and the inorganic oxide film 3. Further, a thin film of a metal oxide formed into amorphous is used as the inorganic oxide 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, a laminated material using the same, and a packaging container. More specifically, the present invention is excellent in transparency, barrier properties against water vapor or oxygen, moisture resistance and the like. Food storage, pharmaceutical packaging, detergents, shampoos, oils,
Transparent barrier film having filling and packaging suitability for various articles in the non-food field such as toothpaste, electronic parts field, etc., further having microwave oven suitability, and excellent in post-processing suitability, and a laminated material using the same. And packaging containers.

[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, among the barrier films as described above, for example, (1) is unsuitable for packaging laminates that require a high gas barrier property, and it is difficult to use chlorine gas or the like during incineration of waste treatment. There is a problem that harmful gas is generated. Next, the method (2) is inferior in moisture resistance, and in particular, has a problem that the oxygen barrier property is dependent on humidity. In the case of (1), there is a problem that the transparency is inferior, the contents cannot be confirmed, and aluminum remains as a slag at the time of incineration of waste treatment, and damages the incinerator and the like. Therefore, for a barrier film as described above, on a flexible plastic substrate, silicon oxide,
There has been proposed a transparent barrier film having a configuration provided with a deposited film of an inorganic oxide such as aluminum oxide, and a packaging laminate using the same. 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. However, the barrier performance of the above-mentioned transparent barrier film and the packaging laminate using the same has a problem that the barrier performance of oxygen, water vapor and the like is inferior to that of the original barrier material of aluminum foil. 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 deposition film in order to improve 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 has found that surface modification is performed by using a plasma gas generated by ionizing a gas by arc discharge. Focusing on the plasma surface treatment to perform, first, on at least one surface of the flexible plastic substrate,
A plasma-treated surface is provided, and a thin film such as a vapor-deposited film of an inorganic oxide is further provided on the plasma-treated surface to produce a transparent barrier film. Thus, the thin film surface of the inorganic oxide of the transparent barrier film Then, at least a heat-sealing resin layer is laminated to produce a laminated material, and the laminated material is used to make a bag or a box to produce a packaging container. When various articles are filled and packaged inside, it has 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.
It has excellent moisture permeability, storage suitability, etc., no cracks during post-processing, and has extremely high post-processing suitability. The present invention has been completed by finding that a transparent barrier film having a packaging suitability for various articles as a packaging material, a laminated material and a packaging container using the same can be produced.

That is, according to the present invention, a plasma treatment surface is provided on at least one surface of a flexible plastic substrate,
Further, the present invention relates to a transparent barrier film, wherein a thin film of an inorganic oxide is provided on the plasma-treated surface, and a laminated material and a packaging container using the same.

[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. FIG. 2, FIG. 3, and FIG. 4 are cross-sectional views showing the layer structure of a laminated material manufactured using the above-described transparent barrier film according to the present invention. 6, FIG. 7,
FIG. 8 and FIG. 9 are plan views or perspective views showing the configuration of a packaging container made from a bag or a box using the laminated material using the transparent barrier film according to the present invention.

The transparent barrier film A according to the present invention comprises:
As shown in FIG. 1, a plasma treatment surface 2 is provided on at least one surface of a flexible plastic substrate 1, and a thin film 3 of an inorganic oxide is further provided on the plasma treatment surface 2. It becomes. Thus, the above examples are examples of the transparent barrier film according to the present invention, and are not limited thereto. For example, although not shown, a plasma-treated surface, a thin film of an inorganic oxide, and the like May be provided on not only one surface but also both surfaces of a flexible plastic substrate.

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. On the surface of the inorganic oxide thin film 3 of the transparent barrier film A shown in FIG.
A laminated material B obtained by laminating the heat-sealing resin layer 4 can be given. Furthermore, as a laminated material according to the present invention, as shown in FIG. 3, at least the substrate film layer 5 is provided on the other surface of the flexible plastic substrate 1 of the laminated material B shown in FIG. A laminated material C obtained by laminating can be exemplified. Alternatively, as a laminated material according to the present invention, as shown in FIG. 4, at least a heat-sealing resin layer 4 is provided on the surface of the base material film layer 5 of the laminated material C shown in FIG.
The laminated material D which laminated | stacked a can be mentioned. 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, In addition to the sealing resin layer and the like, it is possible to design and manufacture various types of laminated materials by arbitrarily laminating other base materials according to the purpose of use and application. . 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, application, etc., the laminate can be laminated at an arbitrary position to design and manufacture laminated materials of various forms.

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 C shown in FIG. 3. As shown in a perspective view of FIG. 5, two laminated materials C and C are prepared. Then, the heat-sealing resin layers 4, 4 located at the innermost layer are superposed on each other so that the surfaces thereof face each other, and then the three sides of the outer peripheral edge are heat-sealed to form a seal portion. 6,
By forming 6, 6, the three-way seal type flexible packaging container E 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 a perspective view of FIG. The attachment portion 7 is overlapped with the other side end portion 9 (shown in FIG. 6), 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.
Furthermore, the upper part is heat-sealed in accordance with a conventional method to form the upper end seal portion 13, so that the roof type paper packaging container F according to the present invention can be manufactured.

Further, as a packaging container according to the present invention, for example, 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 having a sticking portion 7a, and capable of forming a cylindrical body portion is punched and manufactured, and then, FIG.
As shown in the perspective view of FIG.
Is overlapped with the other side end 9a (shown in FIG. 8), 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;
Further, an upper seal portion 19 is formed by heat-sealing, for example, a cylindrical lid plate 18 having a drinking port 17 sealed with a peeling-off piece 16 in an upper portion of the cylindrical container 11a. Thus, the cylindrical paper can-shaped packaging container G according to the present invention can be manufactured by forming the lid 18a. 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 a flexible plastic substrate, a plastic film or sheet capable of holding an amorphous thin film of aluminum oxide is used. Any material can be used as long as it is, for example, polyethylene, polypropylene, polyolefin resin such as polybutene, (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinylidene chloride resin, Saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin, etc. Various resin films or sheets can be used. These resin films or sheets may be uniaxially or biaxially stretched, and have a thickness of about 5 to 500 μm, preferably 12 to 300 μm.
μm is desirable. If necessary, an anchor coat may be formed on the surface of the resin film or sheet if necessary.
A surface smoothing treatment or the like can be performed by coating a coating agent or the like.

Next, in the present invention, the plasma treated surface constituting the transparent barrier film according to the present invention will be described. The plasma treated surface utilizes a plasma gas generated by ionizing a gas by arc discharge. It is possible to form a plasma-treated surface by using a plasma surface treatment method for performing surface modification. In other words, in the present invention, a method using an inorganic gas such as O ₂ (oxygen gas), N ₂ (nitrogen gas), Ar (argon gas), or He (helium gas) as a plasma gas is used. This is for modifying the surface of a plastic substrate. Thus, in the present invention, when forming the plasma-treated surface on the surface of the flexible plastic substrate, O 2 having a small ionization energy is used in the plasma discharge treatment.
₂ (oxygen gas, 12.2 eV)) or a reactive gas consisting of a mixture of O ₂ and N ₂ is preferably used for the plasma treatment.
It is possible to perform plasma treatment at a lower voltage, so that there is no discoloration or the like of the flexible plastic substrate, and further, a polar group such as an O group or an OH group is introduced into the substrate surface by a chemical reaction. This has the advantage that the adhesion between the flexible plastic substrate and the thin film of inorganic oxide can be significantly increased. In the present invention, Ar (15.8 e)
V) and He (24.7 eV) such as He (24.7 eV) can be used to form a plasma processing surface by performing a plasma processing, but in such a case, Ar,
It is necessary to apply a considerable voltage to bring an inert gas such as He into a plasma state, and therefore, the flexible plastic substrate may be thermally degraded, for example, discolored or the like. is not.

In the present invention, the plasma treatment is carried out using a reactive gas such as oxygen gas or a mixed gas of oxygen and nitrogen. The present invention is also applicable to a plasma treatment that directly reacts with the polymer surface constituting the flexible plastic substrate to change the structure of the surface layer. In the present invention, when performing the plasma treatment, the flow rate of the reactive gas composed of O ₂ , or a mixture of O ₂ and N ₂ may be selected according to the width of the flexible plastic substrate and the like. For example, if the width is 600 mm, 100 to 5000 l / mi
The n-position, preferably in the range of 500 to 3000 l / min is desirable. Regarding the plasma processing speed, especially in the limited group, for example, under the conditions of 600 V and 10 A, it is about 50 to 800 m / min, preferably 200 to 800 m / min.
400 m / min is desirable.

Further, in the present invention, as the inorganic oxide thin film constituting the transparent barrier film, basically, any thin film obtained by making a metal oxide amorphous can be used. For example, for example, silicon (S
i), aluminum (Al), magnesium (Mg),
Calcium (Ca), potassium (K), tin (Sn),
Sodium (Na), boron (B), titanium (Ti),
A thin film in which an oxide of a metal such as lead (Pb), zirconium (Zr), or yttrium (Y) is made amorphous can be used. Thus, as a material suitable for a packaging material or the like, a thin film in which an oxide of a metal such as silicon (Si) or aluminum (Al) is made amorphous can be given. Thus, a thin film in which the above metal oxide is made amorphous can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide.
For example, SiO _X, AlO _X, as such as MgO _X MO
_X (wherein, M represents a metal element, and the value of X is
The range differs depending on the metal element. ). The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0-1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
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, is not transparent and cannot be used at all, and the upper end of the range of X is a fully oxidized value. In the present invention, as a packaging material, generally, there are few examples of use other than silicon (Si) and aluminum (Al).
0 and aluminum (Al) 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, depending on the type of metal used, or metal oxide, etc.,
For example, about 50-3000 °, preferably 100-1
It is desirable to form the film by arbitrarily selecting it within the range of about 000 °. Further, in the present invention, the inorganic oxide thin film is not limited to one layer of the inorganic oxide thin film, but may be a laminate of two or more layers. Can be used alone or as a mixture of two or more to form a thin film of an inorganic oxide mixed with different materials.

Next, a method of forming a thin film of an inorganic oxide on a flexible plastic substrate in the present invention will be described. Examples of the method include a vacuum deposition method, a sputtering method, and an ion plating method. Physical Vapor Depth Method (Physical Vapor Depth Method)
chemical vapor deposition (PVD), or a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
(e.g., deposition method, CVD method). In the present invention, when producing a transparent barrier film used for a packaging material, a vacuum deposition method is mainly used, and a plasma chemical vapor deposition method is also partially used. As a specific example, FIG. 10 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine. As shown in FIG. 10, the unwinding roll 11 is placed in the vacuum chamber 111.
The flexible plastic base material 113 fed from Step 2 is
After passing through the heating drum 114 into the vapor deposition chamber-115, the vapor source heated by the crucible 116 is evaporated, and, if necessary, while the oxygen or the like is blown out from the oxygen outlet 117, the above-described process is performed. A flexible plastic substrate on which an inorganic oxide vapor-deposited film is formed via masks 118 and 118 on a flexible plastic substrate 113 on a cooled coating drum 114 and then a vapor-deposited film is formed By sending 113 into the vacuum chamber 111 and winding it around the take-up roll 119, the inorganic oxide thin film according to the present invention can be manufactured.

Further, in the present invention, a method of forming a thin film of an inorganic oxide will be specifically described. The above-described metal oxide is used as a raw material, and is heated to form a thin film on a flexible plastic substrate. Vacuum evaporation method of vapor deposition, oxidation reaction deposition method of using metal or metal oxide as raw material, introducing oxygen and oxidizing and depositing it on flexible plastic substrate, further assisting oxidation reaction with plasma The deposited film can be formed by using a plasma-assisted oxidation reaction deposition method or the like. In the present invention, when a silicon oxide vapor deposition film is formed, the vapor deposition film can be formed by a plasma chemical vapor deposition method using organosiloxane as a raw material.

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

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

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

Next, in the present invention, a method for producing a laminated material using the above-mentioned materials will be described.
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-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, in the packaging container as described above, for example, one-piece type, two-piece type, and other spouts,
Alternatively, a zipper for opening and closing can be optionally attached.

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 On one surface of a biaxially stretched polyethylene terephthalate film (E5102, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm, an oxygen flow rate of 2000 l / min and a voltage of 600 V were applied under the plasma discharge treatment using oxygen gas. , A plasma treatment is performed under the conditions of a current value of 10 A and a treatment speed of 300 m / min to form a plasma treatment surface, and then a vacuum deposition method (see a vapor deposition machine shown in FIG. 10) is applied to the plasma treatment surface. Vacuum evaporation was performed to form a 250-mm-thick aluminum oxide evaporation film, thereby producing a transparent barrier film according to the present invention.

Example 2 One side of a biaxially stretched polyethylene terephthalate film (E5102, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm was subjected to plasma discharge treatment using a mixed gas of oxygen and nitrogen under the treatment conditions. 2000l / mi mixed gas flow
n, voltage 600V, current value 10A, processing speed 300m /
min to form a plasma-treated surface, and then perform vacuum deposition on the plasma-treated surface using a vacuum deposition method (see a vapor deposition machine shown in FIG. 10) to obtain a film thickness of 250 °. Was formed to produce a transparent barrier film according to the present invention.

Example 3 One side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (trade name: E5102, manufactured by Toyobo Co., Ltd.) was subjected to plasma discharge treatment with a mixed gas of oxygen and nitrogen under the treatment conditions. 2000l / mi mixed gas flow
n, voltage 600V, current value 10A, processing speed 300m /
min to form a plasma-treated surface, and then perform vacuum deposition on the plasma-treated surface using a vacuum deposition method (see a vapor deposition machine shown in FIG. 10) to obtain a film thickness of 250 °. Was formed to produce a transparent barrier film according to the present invention.

Comparative Example 1 One side of a biaxially stretched polyethylene terephthalate film (E5102, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm was not subjected to plasma discharge treatment, but was vacuum-deposited on its corona-treated surface. Vacuum deposition was performed using a vacuum deposition method (see a vapor deposition machine shown in FIG. 10) to form a 250 ° -thick aluminum oxide vapor-deposited film, thereby producing a transparent barrier film according to a conventional example.

Experimental Example 1 The transparent barrier films of Examples 1 to 3 and Comparative Example 1 produced above were subjected to the conditions of 25 ° C. and 90% RH.
Oxygen permeability measurement device [model name, OXTRAN 2/2, manufactured by MOCON, USA]
0)] was used to measure the oxygen permeability. Further, the transparent barrier films of Examples 1 to 3 and Comparative Example 1 produced above were subjected to the conditions of 37.8 ° C. and 100% RH.
Mocon Corp., USA, a moisture permeability measuring device [model name, PERMATRAN 3/3
1)] was used to measure the water vapor transmission rate. The above measurement results are shown in Table 1 below.

[0032]

[Table 1]

As is clear from the results shown in Table 1 above, those of Examples 1 to 3 were superior to those of Comparative Example 1 in oxygen permeability and water vapor permeability.

Example 4 A 5% solution of a two-component curable polyester resin was used as a primer on the vapor-deposited surface of the transparent barrier film produced in Example 1 and coated to a thickness of 1 μm. Then, low-density polyethylene was used on the surface of the coating film, which was extruded and coated to a thickness of 60 μm to produce a laminate according to the present invention having the following layer constitution. Biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, plasma treated surface, deposited film of aluminum oxide with a thickness of 250 ° / primer agent layer with a thickness of 1 μm / low-density polyethylene layer with a thickness of 60 μm Use the two pieces, the thickness of 60μ
m low-density polyethylene layers facing each other,
Thereafter, the bag was made by a bag making machine to produce a three-way seal-type plastic bag. Next, the plastic bag prepared above was filled with potato chips, and then the opening was heat-sealed to produce a filled and packaged product. No change in flavor or the like was observed, and very good results were obtained.

Example 5 Next, a primer consisting of a 5% solution of a two-component curable polyester resin was used on the vapor-deposited surface of the transparent barrier film produced in Example 2 above, and this was applied to a thickness of 1 μm. Ni-
Then, low-density polyethylene was used on the surface of the coating film, and was extruded to 80 μm and coated. Further, a low-density polyethylene was used on the biaxially stretched polyethylene terephthalate film surface of the transparent barrier film, which was extruded to a thickness of 100 μm and laminated to form a laminate according to the present invention having the following layer constitution. Lumber was manufactured. Low-density polyethylene layer with a thickness of 100 μm /
12 μm thick bi-stretched polyethylene terephthalate film ・ Plasma treated surface ・ Evaporated film of aluminum oxide 250 μm thick / Primer agent layer 1 μm thick / 80 μm thick
m low-density polyethylene layer Using the laminated material produced above, first, the laminated material is rolled and the overlapped edge is heat-welded to produce a tubular body for forming a tube. A neck was formed at one end of the cylindrical body by injection molding using polypropylene, and a cap was screwed onto the neck to produce a tube container. Next, the contents are filled from the other opening of the tube container,
Thereafter, the opening was heat-sealed to produce a tube-shaped packaged product. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

Example 6 A primer consisting of a 5% solution of a two-component curable polyester resin was used on the vapor-deposited surface of the transparent barrier film produced in Example 3 above, and this was coated to a film thickness of 1 μm. Then, low-density polyethylene was used on the surface of the coating film, which was co-extruded to 80 μm and coated. Next, while extruding a low-density polyethylene with a thickness of 30 μm on the surface of the biaxially stretched polyethylene terephthalate film of the transparent vapor-deposited barrier film, a paper having a basis weight of 200 g / m ² was extruded using a sandwich method. Then, a high-pressure low-density polyethylene was extruded to a thickness of 30 μm on the surface of the paper and laminated to produce three types of laminated materials having the following constitutions. Low-density polyethylene layer having a thickness of 30 μm / paper layer having a basis weight of 200 g / m ² / thickness of 30
μm low-density polyethylene layer / double-stretched polyethylene terephthalate film with a thickness of 12 μm
A silicon oxide deposited film having a thickness of 250 ° / a primer agent layer having a thickness of 1 μm / a low-density polyethylene layer having a thickness of 80 μm Using the laminated material produced above, first, a blank plate for forming a paper container from the laminated material Is manufactured, and the overlapping edge is heat-welded to produce a square body for forming a paper container. Then, one bottom of the square body is folded and sealed to form a bottom. Was formed to produce a paper container. Next, the contents are filled from the opening above the paper container, and then the opening is heat-sealed to form a roof-type upper seal, thereby producing a packaged product. did. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

[0037]

As is apparent from the above description, the present invention focuses on plasma surface treatment for performing surface modification using plasma gas generated by ionizing a gas by arc discharge. A plasma-treated surface is provided on at least one surface of the flexible plastic substrate, and a thin film such as an inorganic oxide vapor-deposited film is provided on the plasma-treated surface to produce a transparent barrier film. Therefore, at least a heat sink is provided on the thin film surface of the inorganic oxide of the transparent barrier film.
A laminated material is manufactured by laminating the sealable resin layers, and further, a bag is made or box-formed using the laminated material to produce a packaging container. Filled and packaged with excellent adhesion between a flexible plastic substrate and a thin film such as a vapor-deposited inorganic oxide film, and has excellent transparency and high barrier properties. It has excellent preservation suitability, has no cracks during post-processing, has extremely high post-processing suitability, and has sufficient microwave oven suitability when packaged products are microwaved. As a material, a transparent barrier film having packaging suitability for various articles, 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 cross-sectional view showing a layer structure of a laminated material manufactured using the transparent barrier film according to the present invention.

FIG. 5 is a perspective view showing the 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. 6 is a plan 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 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. 8 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. 9 is a perspective view showing a configuration of a packaging container formed by bag making or box making using a laminated material using the transparent barrier film according to the present invention.

FIG. 10 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Flexible plastic base material 2 Plasma treated surface 3 Inorganic oxide thin film 4 Heat-sealing resin layer 4a Heat-sealing resin layer 5 Base film layer 6 Seal part 7 Adhering part 8 Blank plate 9 for forming paper container 9 Side end 10 Side seal 11 Body 12 Bottom 13 Upper seal 7a Adhering portion 8a Blank plate 9a for forming paper container 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 plate 18a Lid 19 Upper seal 111 Vacuum chamber 112 Unwinding roll -Roll 113 Flexible plastic substrate 114 Coating drum 115 Deposition chamber-116 Crucible 117 Oxygen outlet 118 Mask 119 Winding roll A Transparent barrier film B Laminate C Layer material D laminate E Mikatashi - le type flexible packaging container F roof type paper packaging container G cylindrical paper can-shaped packaging containers l Orikei

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 7/04 C08J 7/04 P

Claims (13)

[Claims] 1. A transparent barrier film, comprising: a plasma-treated surface provided on at least one surface of a flexible plastic substrate; and a thin film of an inorganic oxide provided on the plasma-treated surface. 2. The transparent surface according to claim 1, wherein the plasma treatment surface is a plasma treatment surface using an inorganic gas composed of O ₂ , a mixture of O ₂ and N ₂ as a plasma gas. Barrier film. 3. The transparent barrier film according to claim 1, wherein the inorganic oxide thin film comprises a silicon oxide or aluminum oxide thin film. 4. A transparent barrier film comprising: a plasma treated surface provided on at least one surface of a flexible plastic substrate; and a thin film of an inorganic oxide provided on the plasma treated surface; A laminate comprising a heat-sealing resin layer laminated on a thin film of an inorganic oxide. 5. The laminated material according to claim 4, wherein a base film is laminated on the other surface of the transparent barrier film. 6. The method according to claim 6, further comprising the step of:
The laminated material according to claim 5, wherein the laminated material is formed by laminating a plurality of conductive resin layers. 7. The plasma processing surface according to claim 4, wherein the plasma processing surface is a plasma processing surface using an inorganic gas composed of O ₂ , a mixture of O ₂ and N ₂ as a plasma gas. The laminated material described in. 8. The laminated material according to claim 4, wherein the inorganic oxide thin film comprises a silicon oxide or aluminum oxide thin film. 9. A transparent barrier film comprising: a plasma treatment surface provided on at least one surface of a flexible plastic substrate; and a thin film of an inorganic oxide provided on the plasma treatment surface; A packaging container characterized by using a laminated material comprising a heat-sealing resin layer laminated on a thin film of an inorganic oxide, and forming or laminating the laminated material. 10. The packaging container according to claim 9, wherein a base film is laminated on the other surface of the transparent barrier film. 11. The packaging container according to claim 10, wherein a heat-sealing resin layer is further laminated on the base film. 12. The plasma processing surface is composed of O ₂ , O ₂ and N _2.
12. The packaging container according to claim 9, wherein the packaging container comprises a plasma-treated surface using an inorganic gas composed of a mixture of the above as a plasma gas. 13. The packaging container according to claim 9, wherein the inorganic oxide thin film comprises a silicon oxide or aluminum oxide thin film.