JPH11105190A - Transparent barrier film, and laminated body and container for package using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate yellowing, to improve adhesive strength, to provide high barrier properties and to improve transparency by providing a barrier layer consisting of a thin film of an inorg. oxide prepd. by a plasma chem. gas phase growing method on one face of a sealant base material. SOLUTION: This transparent barrier film 1 has a constitution provided with a barrier layer 4 consisting of an inorg. oxide thin film 3 by a plasma chem. gas phase growing method on one face of a sealant base material 2. As the sealant base material 2, a polyolefin resin with heat-sealability is used and it consists of two or more coextrusion laminated body films. As the inorg. oxide thin film based on the plasma chem. gas phase growing method, a metallized film of silica by the plasma chem. gas phase growing method can be used. As the film thickness of the metallized film of silica, about 100-300 Åis more pref.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a transparent barrier film, a laminate using the same, and a packaging container.
More specifically, it has excellent transparency, and further has a high barrier property against oxygen gas or water vapor, etc.
The present invention relates to a transparent barrier film suitable for filling and packaging of various articles such as pharmaceuticals, cosmetics, chemicals, electronic products, miscellaneous goods, and the like, and a laminate and a packaging container using the same.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, and others. Among them, in recent years,
As a barrier material against oxygen gas or water vapor, on the surface of the plastic substrate, for example, a vacuum deposition method,
Physical vapor deposition (PVD) such as sputtering and ion plating, or chemical vapor deposition (CVD) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. ) And the like, a transparent gas barrier film formed by forming a deposited film of an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like has attracted attention. In the transparent gas barrier film, the plastic substrate may be, for example, 2
It has been proposed to use a resin film such as an axially stretched polyethylene terephthalate film, a nylon film, a biaxially stretched polypropylene film, or a saponified ethylene-vinyl acetate copolymer film.

[0003]

However, in the above transparent gas barrier film, when a biaxially oriented polypropylene film is used as a plastic substrate, the biaxially oriented polypropylene film includes, for example,
Since it contains additives and fillers for preventing blocking, etc., its surface has a fine uneven shape, and therefore, the surface smoothness is reduced by other substrates (biaxial stretching). (Polyethylene terephthalate film, biaxially stretched nylon film, etc.) is inferior. As a result, it is difficult to form an inorganic oxide vapor-deposited film on one surface, and a vapor-deposited film that completely covers the surface continuously is formed. It is extremely difficult to produce a transparent gas barrier film that is sufficiently satisfactory. Also, 2
Using an axially stretched polypropylene film, on one side,
When forming an inorganic oxide deposited film such as a silicon oxide deposited film by plasma enhanced chemical vapor deposition, the biaxially stretched polypropylene film is yellowed or browned by plasma treatment, and further, There is also a problem that it is extremely difficult to produce a colorless and transparent barrier biaxially oriented polypropylene film which is chemically deteriorated. Further, when a biaxially stretched polypropylene film is used and a vapor-deposited film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed on one surface by plasma enhanced chemical vapor deposition, the surface of the biaxially-stretched polypropylene film is In addition, a layer (weak boundary) in which a so-called adhesive property is weakened by plasma treatment
(Layer WBL) is generated, which causes a problem that the adhesion strength between the biaxially stretched polypropylene film and the deposited film of the inorganic oxide is insufficient, and the barrier property is not improved. Further, biaxially stretched polypropylene film is inferior in heat resistance, for example, by physical vapor deposition,
When a deposited film of an inorganic oxide is formed, a phenomenon that the film itself is deteriorated by heat and a transparent gas barrier film can no longer be produced often occurs. Further, in the above-mentioned transparent gas barrier film, generally, printing is performed on the surface of the deposited film of the inorganic oxide which is the base film, and at this time, the base film is passed through to the winding side of a printing machine. In addition, a large amount of unusable film occurs due to ink or ink adjustment. Also, in the laminating process, the base film passes through the coater to the take-up side. This can cause high costs. Therefore, the present invention uses a biaxially stretched polypropylene film as a base material, yellowing, or browning, furthermore, without chemically deteriorating, furthermore, its adhesion strength is excellent, oxygen gas or A transparent gas barrier that has a high barrier property against water vapor and the like, and has excellent transparency, and is useful as a packaging material for various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic components, sundries, and others. An object of the present invention is to provide a conductive film, a laminate using the same, and a packaging container.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has found that a biaxially oriented polypropylene is used as a plastic substrate when forming an inorganic oxide deposition film. Instead of using a film, attention was paid to using a sealant substrate having excellent surface smoothness. Therefore, one surface of the sealant substrate was coated with a plasma chemical vapor deposition method or the like. To form a vapor-deposited film of an inorganic oxide, whereby the vapor-deposited film of an inorganic oxide is continuously, uniformly, and completely covered on the surface of the sealant substrate. The biaxially stretched polypropylene film may be laminated on the surface of the inorganic oxide vapor-deposited film of the sealant substrate having the inorganic oxide vapor-deposited film, for example, by plasma chemical vapor deposition. Inorganic oxide deposited film by phase growth method When forming, to prevent yellowing or browning of the surface of the biaxially oriented polypropylene film, furthermore, to prevent chemical or thermal deterioration, and to laminate the biaxially oriented polypropylene film as described above. Thereby, indirectly, it is possible to form a deposited film of an inorganic oxide that completely covers the surface, and further, when laminating, by laminating via a laminating adhesive or the like, the deposited film of the inorganic oxide can be formed. Manufacture of a transparent barrier film having improved adhesion strength and, ultimately, transparency, which can sufficiently satisfy a barrier property against oxygen gas or water vapor, a laminate and a packaging container using the same. It has been found that the present invention has been completed and the present invention has been completed.

That is, the present invention relates to a transparent barrier film characterized in that it has a barrier layer comprising a thin film of an inorganic oxide formed by plasma enhanced chemical vapor deposition on one surface of a sealant substrate, and a transparent barrier film comprising the same. 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 the transparent barrier film according to the present invention, a laminated body and a packaging container using the same will be described with reference to the drawings, illustrating a few examples thereof.
1 and 2 are cross-sectional views showing a layer configuration of one example of the transparent barrier film according to the present invention. FIGS. 3 and 4 show the case where the transparent barrier film according to the present invention is used. And FIG. 5, FIG. 6, FIG. 7, FIG. 8 and FIG. 9 are cross-sectional views showing a layer structure using the transparent barrier film according to the present invention. FIG. 2 is a plan view or a perspective view showing a configuration of a packaging container formed by bag making or box making using a body.

The transparent barrier film 1 according to the present invention
As shown in FIG. 1, a basic configuration is such that a barrier layer 4 made of a thin film 3 of an inorganic oxide is provided on one surface of a sealant substrate 2 by a plasma enhanced chemical vapor deposition method. It consists of As another example of the transparent barrier film according to the present invention, as shown in FIG. 2, in the transparent barrier film 1 shown in FIG. Uses a polyolefin resin having heat sealability,
Or extruded laminate film 2a comprising
And a thin film 3 of an inorganic oxide formed by plasma enhanced chemical vapor deposition on one surface of the co-extruded laminate film 2a.
A transparent bright barrier film 1a having a configuration in which a barrier layer 4 is provided may be used. In the present invention, the above examples illustrate one example of the transparent barrier film according to the present invention, and the present invention is not limited thereto. It may be provided not only on one surface of the runt substrate but also on both surfaces.

Next, the laminate manufactured using the transparent barrier film according to the present invention will be described by way of example.
For example, as shown in FIG. 3, a base film 5 is laminated on the surface of the barrier layer 4 composed of the inorganic oxide thin film 3 of the transparent barrier film 1 shown in FIG. Can be mentioned. Further, as shown in FIG. 4, the laminate according to the present invention further comprises a polyolefin having at least heat sealability on the surface of the base film 5 of the laminate A shown in FIG. A laminate B in which the resin layers 6 are laminated can be given. Thus, the above-mentioned examples are only examples of one example constituting the laminate according to the present invention, and the present invention is not limited to these examples. In addition to a film, a polyolefin-based resin layer having heat sealability, etc., other base materials may be arbitrarily laminated according to the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the application, and the like. Thus, various forms of laminates can be designed and manufactured. In the present invention, the base film layer, the polyolefin-based resin layer having heat sealability, and the other layers may be arbitrarily laminated according to the purpose of use, application, and the like. 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 laminate to form a bag or a box, will be described. By exemplifying and explaining a packaging container made from a bag or a box using the laminate material A shown in FIG. 3, two laminates A and A are prepared as shown in a perspective view of FIG. And the sealant substrate 2 located in the innermost layer,
Then, the three sides of the outer peripheral edge are heat-sealed to seal portions 7, 7, 7
The three-way seal type flexible packaging container C 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, using a laminated material B shown in FIG.
(Indicated by a dotted line), a blank plate 9 for forming a paper container having a sticking portion 8 and the like is manufactured by punching, and then, as shown in a perspective view of FIG. The attachment portion 8 is overlapped with the other side end portion 10 (shown in FIG. 6), and the overlapped portion is heat-sealed to form a side end seal portion 11 to produce a body portion 12, and The lower portion of the body 12 is folded in a conventional manner to form a heat seal to form a bottom portion 13, and the upper portion thereof is heat-sealed in a conventional manner.
Then, the roof type sealing portion 14 is formed to manufacture the roof type paper packaging container D according to the present invention.

Further, as a packaging container according to the present invention, for example, as shown in the plan view of FIG.
First, a blank material 9a for forming a rectangular paper container, which has a sticking portion 8a and the like and is capable of forming a cylindrical body, is punched out from the laminated material B shown in FIG. FIG.
As shown in the perspective view of FIG.
Is overlapped with the other side end portion 10a (shown in FIG. 8), and the overlapped portion is heat-sealed to form a side end seal portion 11a to produce a cylindrical body portion 12a. The cylindrical body 12
For example, the bottom portion 15a is formed by heat-sealing a cylindrical bottom plate 15 to form a bottom seal portion 16 at a lower portion of the lower portion a. ,
Heat sealing a cylindrical lid plate 19 having a drinking opening 18 sealed with a peeling off piece 17 to form an upper seal portion 20
Is formed to form the lid 19a, and the cylindrical paper can-shaped packaging container E according to the present invention can be manufactured. In the present invention, it is needless to say that the present invention is not limited to the above-illustrated packaging container, and that various types of packaging containers can be manufactured depending on the purpose, application, and the like. Needless to say.

Next, in the present invention, the materials constituting the transparent barrier film, the laminate, the packaging container and the like according to the present invention as described above, and the production methods thereof will be described. , Various things can be adopted. First, in the present invention, a material constituting the transparent barrier film according to the present invention will be described. First, as a sealant substrate, a barrier layer composed of a thin film of an inorganic oxide is formed by a plasma enhanced chemical vapor deposition method. Further, a resin film or sheet that can be fused and mutually fused 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, methylpentene polymer, polybutene Acid-modified polyolefin resin obtained by modifying polyolefin resin such as limmer, polyethylene or polypropylene with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate Films or sheets of various resins such as a resin, a poly (meth) acrylic resin, a polyvinyl chloride resin and others can be used.

Thus, in the present invention, the above resin film or seal as the sealant substrate is used.
The thickness of the gate can be appropriately set in consideration of the stability at the time of manufacture, etc., but is preferably about 10 μm to 100 μm, more preferably about 20 μm to 50 μm. In the present invention, the above-mentioned sealant base material preferably has a surface roughness having a surface roughness within a range of 1.4 μm or less in terms of 10-point average roughness. It is possible that the deposited film completely covers the surface of the substrate,
This is because the necessary barrier properties can be sufficiently obtained. Further, in the present invention, as the sealant substrate,
It is preferable to have transparency from the viewpoint that the contents can be seen. Furthermore, in the present invention, among the above-mentioned sealant base materials, it is particularly preferable to use an unstretched polypropylene film, which has heat resistance among the sealant base materials, and further has a sealant. sex,
This is because they are also excellent in oil resistance, transparency, and the like.
Further, in the present invention, as the sealant substrate,
The above-mentioned heat-sealable polyolefin-based resins are used, and a combination of two or more of these resins is used, for example, by T-die coextrusion or coextrusion inflation. A co-extruded laminate film obtained by co-extrusion using a molding method or the like can be used. In this case, it is preferable that the film has an advantage that it has excellent barrier properties, transparency, and the like, and has sufficient heat sealability.

Next, in the present invention, a thin film of an inorganic oxide formed by plasma enhanced chemical vapor deposition as a barrier layer will be described. Alternatively, a deposited film (thin film) of silicon oxide formed by a plasma enhanced chemical vapor deposition method can be used. Thus, as the silicon oxide vapor-deposited film formed by the above-mentioned plasma chemical vapor deposition method, the formula SiO _x (X
Is a continuous vapor-deposited film mainly composed of silicon oxide represented by a number from 0 to 2). Further, from the viewpoint of transparency, barrier properties and the like, the formula SiO _x (X is 1.7) It is preferably a thin film mainly composed of a deposited silicon oxide film represented by the following formula: The silicon oxide vapor-deposited film has at least silicon and oxygen as constituent elements, and further includes a silicon oxide vapor-deposited film containing a trace constituent element of at least one of carbon, hydrogen, and oxygen. . Further, it is desirable that the above-mentioned silicon oxide vapor-deposited film is a silicon oxide vapor-deposited film containing carbon and having a reduced carbon content in the depth direction of the vapor-deposited film. In the present invention, the thickness of the deposited silicon oxide film is preferably not more than 400 °, specifically, about 50 to 400 °, more preferably 100 to 300 °. Position is desirable, so
In the above description, if the thickness is more than 400 ° or more than 300 °, cracks or the like are easily generated in the film, which is not preferable. If the thickness is less than 100 ° or further less than 50 °, it is difficult to exhibit the effect of the barrier property. This is undesirable because

In the present invention, the above-mentioned silicon oxide vapor-deposited film is specifically formed by a plasma chemical vapor deposition method using an organic silicon compound as a raw material and utilizing a low-temperature plasma generator or the like. A deposited film of silicon oxide can be used. The above-described plasma chemical vapor deposition method will be described more specifically with reference to an example.
As shown in the schematic configuration diagram of FIG. 0, a sealant substrate 114 unwound from an unwinding roll 113 disposed in a vacuum chamber 112 of a plasma chemical vapor deposition apparatus 111 passes through an auxiliary roll 115. While being conveyed at a constant speed, a mixed gas composed of an organic silicon compound, oxygen gas, inert gas, or the like supplied from the raw material volatile supply devices 117, 118, 119 is supplied on the peripheral surface of the cooling / electrode drum 116. Introduced through the nozzle 120, a glow discharge plasma 121 is used to form a deposited silicon oxide film on the sealant substrate 114 to form a film. A predetermined voltage is applied from a power supply 122 disposed outside, and
A magnet 123 is provided near the cooling / electrode drum 116.
Is disposed to promote the generation of plasma. Then, the sealant substrate 114 on which the silicon oxide vapor-deposited film is formed is wound up on a winding roll 124 via an auxiliary roll 115. The transparent barrier film according to the present invention can be manufactured. In the drawing, reference numeral 125 denotes a vacuum pump.

In the above, as the organosilicon compound,
For example, 1.1.3.3-tetramethyldisiloxane,
Hexamethyldisiloxane, vinyltrimethylsilane,
Methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethylsilane Ethoxysilane, octamethylcyclotetrasiloxane, and others can be used. In the present invention, among the above-mentioned organosilicon compounds, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its characteristics and the like. Further, in the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used. In order to obtain the above, it is desirable to use a generator using a high-frequency plasma method.

The transparent barrier film according to the present invention comprises:
As described above, on one surface of the sealant substrate, a vapor-deposited inorganic oxide film is formed as a barrier layer by plasma enhanced chemical vapor deposition to enable production of a transparent barrier film having high barrier properties. Things. In the present invention,
By using a sealant substrate having excellent smoothness, in particular, an unstretched polypropylene film, and forming an inorganic oxide deposited film by plasma enhanced chemical vapor deposition as a barrier layer on one surface thereof. Compared to a biaxially stretched polypropylene film having poor smoothness, there is an advantage that an inorganic oxide vapor-deposited film is easily formed, and further, the substrate surface can be completely covered, and a barrier property is extremely improved. It has. Furthermore, in the present invention, the sealant base material, for example, an unstretched polypropylene film is inferior in heat resistance like a biaxially stretched polypropylene film, so that it can be deposited at a low temperature by a plasma enhanced chemical vapor deposition method. It is to form a deposited film of an inorganic oxide, thereby, for example, deterioration or heat shrinkage of the substrate caused when forming a deposited film of the inorganic oxide using a physical vapor deposition method or the like, This prevents a reduction in barrier properties and the like. Further, in the present invention, by forming a vapor-deposited film of an inorganic oxide on a sealant substrate, a substrate film or the like is laminated on the surface of the vapor-deposited film of the inorganic oxide to form a laminate as a packaging material. Since a base film is produced, unlike a base film that generates a large amount of unusable film in the printing or laminating process, the sealant base on which the vapor-deposited film is placed must be used without waste. It is excellent in cost. Thus, in the present invention, the transparent barrier film according to the present invention has an oxygen permeability of 1
It is preferably at most 0 cc / m ² / day (23 ° C./90% RH).

Next, in the present invention, the base film constituting the laminate is, for example, a basic material when constituting a packaging container, so that it is mechanically, physically,
Chemical, has excellent properties in other, etc., in particular, can be used a resin film or sheet that is strong and tough, and has heat resistance, specifically,
For example, films or sheets of tough resins such as polyester resins, polyamide resins, polyaramid resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyacetal resins, fluorine resins, and others. -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 5 μm to 10
It is desirably about 0 μm, preferably about 10 μm to 50 μm. 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, for example, various paper base materials constituting a paper layer can be used.
The paper base material is provided with shapeability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard, A paper substrate such as a processed paper or the like can be used. In the above, the paper base constituting the paper layer has a basis weight of about 80 to
600 g / m ² , preferably about 100-200 g / m ²
It is desirable to use a material of about 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.

In the present invention, among the above-mentioned base films, it is particularly preferable to use a biaxially oriented polypropylene film. A polypropylene-based resin film or sheet formed of a copolymer with another monomer or a copolymer with another monomer may be used. The resin film or sheet can be used as a single layer or a film formed by a co-extrusion method of two or more layers. About 10 to 10 due to stability
It is desirably about 0 μm, preferably about 20 to 50 μm.

Next, in the present invention, the polyolefin-based resin constituting the heat-sealing polyolefin-based resin layer forming the laminate may be a resin that can be melted by the above-mentioned heat and fused to each other. Films or sheets 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 Polyolefin resin such as polymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene was modified with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Acid-modified polyolefin resin,
Polyvinyl acetate resin, poly (meth) acrylic resin,
Films or sheets of various resins such as polyvinyl chloride resins and others 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 or film or sheet is 5μ.
m to 300 μm, more preferably 10 μm
About 100 μm is desirable.

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

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet 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 laminate using the above-mentioned materials in the present invention will be described. As the method, a conventional packaging material is laminated.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pre-treatment such as a corona treatment, an ozone treatment, a framing treatment, or the like can be performed on the film. Anchor coating agents such as polyester, isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate And known adhesives such as adhesives for laminates such as cellulose, cellulose, etc.
Coating agents, adhesives and the like can be used.

Next, in the present invention, a method for producing a bag or a box using the above-mentioned laminate will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using the laminated body manufactured by such a method, the heat-sealing resin layer of the inner layer is opposed to the laminated body, and the heat-sealing resin layer is folded, or the two sheets are overlapped, and the peripheral end portion is further folded. A bag can be formed by providing a seal portion by heat sealing. Thus, as a bag making method, the above-mentioned laminate 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 obtained by laminating a paper substrate 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 produced as described above is excellent in transparency, barrier properties against oxygen, water vapor, etc., impact resistance, and the like. It has the suitability for post-processing such as box making, and also prevents peeling of the deposited thin film as a barrier film, and also prevents the occurrence of thermal cracks, and prevents its deterioration, and Demonstrates excellent resistance, for example, filling of various goods such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, etc., chemicals or cosmetics, electronic components, sundries, etc. It has excellent packaging suitability and storage suitability.

[0028]

【Example】

Example 1 (1). An unstretched polypropylene film having a thickness of 25 μm was used, and this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a deposited silicon oxide film having a thickness of 120 ° was formed under the following conditions. Such a transparent barrier film was produced. Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 The degree of vacuum in a vacuum chamber: 5.0 × 10 ⁻⁶ mbar The degree of vacuum in a deposition chamber: 6.0 × 10 ^{− 2} mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 130 m / min Evaporation surface: Corona treated surface Evaporation film thickness: 120 mm (X-ray fluorescence analysis) (2). The corona treatment was performed on the surface of the silicon oxide vapor-deposited film of the transparent barrier film produced above under the following conditions.
As a result, the surface tension of the surface of the deposited silicon oxide film was 41
dyn was improved to 62 dyn. Output: 10 Kw Processing speed: 100 m / min (3). Next, a biaxially stretched polypropylene film having a thickness of 20 μm was used, which was mounted on one of the delivery rolls of a dry laminator coater. On the other hand, the corona-treated transparent barrier film was treated with the above-mentioned transparent barrier film. Dry laminating
The biaxially-stretched polypropylene film was attached to the other delivery roll of the tocotor machine, and then the corona-treated surface of the corona-treated transparent barrier film was opposed to the corona-treated surface. Dry lamination was carried out under the conditions to produce a laminate according to the present invention. Adhesive: Use urethane-based adhesive (Main agent) Takenet A-515 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Curing agent) Takenet A-50 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Solvent) Ethyl acetate (Mixing ratio) Main agent: Curing agent: Solvent = 10: 1: 100 (% by weight) (Coating amount) 4.0 g / m ² (Dry)

Comparative Example 1 (1). A biaxially stretched polypropylene film having a thickness of 20 μm was used, which was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a deposited film of silicon oxide having a thickness of 140 ° was formed under the following conditions to form a transparent barrier. A conductive film was produced. Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 The degree of vacuum in a vacuum chamber: 5.0 × 10 ⁻⁶ mbar The degree of vacuum in a deposition chamber: 6.0 × 10 ^{− 2} mbar Cooling / electrode drum supply power: 22 kW Film transport speed: 100 m / min Evaporation surface: Corona treated surface Evaporation film thickness: 140 ° (X-ray fluorescence analysis) (2). The corona treatment was performed on the surface of the silicon oxide vapor-deposited film of the transparent barrier film produced above under the following conditions.
As a result, the surface tension of the surface of the deposited silicon oxide film was 39
dyn was improved to 60 dyn. Output: 10 Kw Processing speed: 100 m / min (3). Next, an unstretched polypropylene film having a thickness of 25 μm was used, and this was attached to one of the delivery rolls of a dry laminator coater. On the other hand, the transparent barrier film subjected to the above corona treatment was treated with the above dry laminating film. -Attach it to the other delivery roll of the toe coater, then
On the corona-treated surface of the corona-treated transparent barrier film, the unstretched polypropylene film was opposed to the corona-treated film, and both were dry-laminated under the following conditions.
A laminate was manufactured. Adhesive: Use urethane-based adhesive (Main agent) Takenet A-515 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Curing agent) Takenet A-50 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Solvent) Ethyl acetate (Mixing ratio) Main agent: Curing agent: Solvent = 10: 1: 100 (% by weight) (Coating amount) 4.0 g / m ² (Dry)

Experimental Example The following data was measured for each transparent barrier film and each laminate produced in Example 1 and Comparative Example 1 described above. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of Water Vapor Permeability This is a condition of a temperature of 40 ° C. and a humidity of 100% RH.
Matran (PERMATRAN)]. (3). Measurement of Surface Smoothness This was measured for an unstretched polypropylene film having a thickness of 25 μm as a sealant substrate and a biaxially stretched polypropylene film having a thickness of 20 μm. The measurement was performed using a three-dimensional surface roughness measuring device (model name, Surfcom 590A-3DF, manufactured by Tokyo Seimitsu Co., Ltd.). The surface roughness was evaluated by a 10-point average value (Rs). The measurement results of the above (1) and (2) are shown in Table 1 (for the film made of a transparent barrier) and Table 2 (for the laminate), and for the measurement results of the above (3), It is shown in Table 3 below.

[0031]

[Table 1] In Table 1 above, the oxygen permeability is cc / m ² / da
The unit is y · 23 ° C. · 90% RH, and the water vapor permeability is the unit of g / m ² / day · 40 ° C. · 100% RH.

[0032]

[Table 2] In Table 2 above, the oxygen permeability is cc / m ² / da
The unit is y · 23 ° C. · 90% RH, and the water vapor permeability is the unit of g / m ² / day · 40 ° C. · 100% RH.

[0033]

[Table 3]

As is clear from the results shown in Tables 1 and 2, the transparent barrier film and the laminate of Example 1 had good oxygen permeability and water vapor permeability in both cases. On the other hand, those of Comparative Example 1 were all inferior. In particular, a significant difference in oxygen permeability was observed between Example 1 and Comparative Example 1. From the above, it was found that forming an inorganic oxide vapor-deposited film on the sealant film was more excellent in oxygen permeability and water vapor permeability. Next, as is clear from the results shown in Table 3 above, it was confirmed that the smoothness of the unstretched polypropylene fill was higher than that of the biaxially stretched polypropylene film.

[0035]

As is apparent from the above description, the present invention provides a method for forming a vapor-deposited film of an inorganic oxide, instead of using a biaxially-stretched polypropylene film as a plastic substrate, to improve surface smoothness. Focusing on the use of an excellent sealant base material, the inorganic oxide deposited film is formed on one surface of the sealant base material by using a plasma enhanced chemical vapor deposition method or the like. Is formed, whereby a deposited film of an inorganic oxide is continuously and uniformly formed on the surface of the sealant substrate.
In addition, the biaxially stretched polypropylene film can be formed so as to completely cover the surface thereof, and is further laminated on the inorganic oxide deposited film surface of the sealant base having the inorganic oxide deposited film. By this, for example, when forming an inorganic oxide deposited film by plasma enhanced chemical vapor deposition,
Yellowing or browning of the surface of the biaxially oriented polypropylene film, and furthermore, preventing chemical or thermal deterioration, etc., and indirectly by laminating the biaxially oriented polypropylene film as described above It is possible to form a deposited film of an inorganic oxide that completely covers the surface,
At the time of lamination, by laminating through a laminating adhesive or the like, the adhesion strength of the inorganic oxide vapor-deposited film is improved, and ultimately, it has transparency and has a sufficient barrier property against oxygen gas or water vapor. A transparent barrier film satisfying the above conditions, and a laminate and a packaging container using the same can be produced. In the present invention, in particular, even when an inorganic oxide vapor-deposited film is formed on the surface of a biaxially stretched polypropylene film having poor surface smoothness by a plasma enhanced chemical vapor deposition method, a sufficient barrier property against oxygen gas or water vapor is obtained. Although not obtained, by forming an inorganic oxide deposited film by plasma enhanced chemical vapor deposition on the surface of an unstretched polypropylene film having excellent surface smoothness, excellent barrier properties against oxygen gas or water vapor, In particular, the present invention has an advantage that a transparent barrier film having an excellent barrier property against oxygen gas can be produced. Further, in the present invention, an inexpensive vapor deposition material such as an organic silicon compound is used, and further, at a low vacuum, a plasma enhanced chemical vapor deposition method is used to form an inorganic oxide vapor deposition film. This reduces the manufacturing cost. Further, in the present invention, since a vapor-deposited film of an inorganic oxide is formed on the surface of a sealant film such as an unstretched polypropylene film, for example, a vapor-deposited film of an inorganic oxide is formed on the surface of a biaxially stretched polypropylene film or the like. Compared to forming, it is excellent in barrier property or cost.

[Brief description of the drawings]

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

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

FIG. 3 is a cross-sectional view showing a layer structure of an example of a laminate manufactured using the transparent barrier film according to the present invention.

FIG. 4 is a cross-sectional view showing a layer configuration of an example of a laminate manufactured using the transparent barrier film according to the present invention.

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

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

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

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

FIG. 9 is a perspective view showing a 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.

FIG. 10 is a configuration diagram showing a schematic configuration of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent barrier film 1a Transparent barrier film 2 Sealant base material 3 Inorganic oxide thin film 4 Barrier layer 5 Base film 6 Polyolefin resin layer having heat seal property 7 Seal part 8 Adhesion Part 9 Blank plate for paper container formation 10 Side end 11 Side end seal part 12 Body part 13 Bottom part 14 Roof type seal part 8a Sticking part 9a Blank plate for paper container formation 10a Side end part 11a side End seal portion 12a Cylindrical trunk portion 15 Cylindrical bottom plate 15a Bottom portion 16 Bottom seal portion 17 Peeling piece 18 Drinking port 19 Cylindrical lid plate 19a Lid portion 20 Upper seal portion A Laminated body B Laminated Body C Three-way seal type soft packaging container D Roof type paper packaging container E Cylindrical paper can-shaped packaging container l Folded crease

Claims (14)

[Claims] 1. A transparent barrier film comprising a structure in which a barrier layer comprising a thin film of an inorganic oxide formed by plasma enhanced chemical vapor deposition is provided on one surface of a sealant substrate. 2. The transparent material according to claim 1, wherein the surface roughness of the sealant substrate has a surface smoothness within a range of 1.4 μm or less in terms of a 10-point average roughness Rs. Barrier film. 3. The transparent barrier film according to claim 1, wherein the sealant substrate is an unstretched polypropylene film. 4. The method according to claim 1, wherein the sealant substrate is formed of a co-extruded laminated film comprising two or more polyolefin resins having heat sealability. Or the transparent barrier film described in 3. 5. A barrier layer comprising a thin film of an inorganic oxide,
A barrier layer composed of a silicon oxide thin film, wherein the silicon oxide thin film further contains at least one compound composed of one or more elements of carbon, hydrogen, silicon or oxygen. The transparent barrier film according to claim 1, 2, 3, or 4, wherein: 6. A barrier layer comprising a thin film of silicon oxide,
The transparent barrier film according to claim 5, which is a barrier layer comprising a silicon oxide vapor-deposited film formed by a plasma enhanced chemical vapor deposition method. 7. A barrier layer comprising a deposited film of silicon oxide, comprising silicon and oxygen as constituent elements, and further containing at least one element of carbon, hydrogen, or oxygen as a trace constituent element. The transparent barrier film according to claim 6, wherein the film is a transparent barrier film. 8. A barrier layer comprising a thin film of an inorganic oxide,
3. The method according to claim 1, further comprising carbon, wherein the amount of carbon decreases in the depth direction of the barrier layer.
8. The transparent barrier film described in 3, 4, 5, 6 or 7. 9. A barrier layer comprising a thin film of an inorganic oxide,
The transparent barrier film according to claim 1, wherein the film thickness is 400 ° or less. 10. An oxygen permeability of 10 cc / m ² / da
y (23 ° C./90% RH) or less.
4. The transparent barrier film described in 1. 11. A transparent barrier film having a barrier layer formed of a thin film of an inorganic oxide by plasma enhanced chemical vapor deposition on one surface of a sealant substrate,
A laminate comprising a structure in which substrate films are laminated. 12. The method according to claim 11, wherein the base film is a biaxially stretched polypropylene film.
The laminate described in the above. 13. The laminate according to claim 11, wherein a polyolefin-based resin layer having heat sealability is further provided on the base film. 14. A transparent barrier film having a barrier layer composed of a thin film of an inorganic oxide formed by plasma enhanced chemical vapor deposition on one surface of a sealant substrate,
Using a laminate consisting of laminated base film,
A packaging container characterized by being made into a bag or a box.