JP2000272044A - Transparent barrier film, method and apparatus for producing the same and laminated material and packaging container using transparent barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent barrier film excellent in oxygen barrier properties, transparency and impact resistance, an apparatus for producing the same, a laminated material having post-processing aptitude and a packaging container good in the filling and packaging aptitude of contents. SOLUTION: After a substrate film is preheated, a barrier layer being a membrane based on silicon oxide [SiOY (1.5<=Y<=2)] formed by an ion plating method using SiOX (0<=X<=2) as an evaporation source and having oxygen permeability of 0.02-0.5 cc/m2.day is formed on at least one surface of the substrate film to constitute a transparent barrier film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent barrier film, an apparatus for producing the same, and a laminated material and a packaging container using the same, and particularly excellent barrier properties against oxygen gas and water vapor, transparency and impact resistance. The present invention relates to a transparent barrier film having properties, a method for producing the same, a production apparatus, and a laminated material and a packaging container having excellent storage suitability and post-processing suitability using the present transparent barrier film.

[0002]

2. Description of the Related Art Conventionally, various materials have been developed and proposed as packaging materials having a barrier property against oxygen gas and water vapor and having good storage suitability for foods, medical products and the like. , A transparent barrier film composed of a coating layer of polyvinylidene chloride or ethylene vinyl alcohol copolymer on a flexible plastic substrate, or silicon oxide, aluminum oxide, etc. on a flexible plastic substrate There has been proposed a transparent barrier film having a configuration provided with an inorganic oxide vapor-deposited film, and a packaging laminate and a packaging container using the same.

[0003] These materials are excellent in transparency as compared with conventional laminated materials for packaging using aluminum foil or the like, and at the same time, have high barrier properties against water vapor, oxygen gas, etc. The demand for packaging materials, etc. is greatly expected.

[Problems to be solved by the invention]

However, among the above-mentioned transparent barrier films and packaging laminates using the same, the transparent barrier film provided with a coating layer of polyvinylidene chloride or ethylene vinyl alcohol copolymer has a barrier against oxygen and water vapor. However, there is a problem in that the barrier property is not sufficiently high, and particularly in the sterilization treatment at a high temperature, the barrier property is significantly reduced. Furthermore, a transparent barrier film provided with a polyvinylidene chloride coating layer generates toxic dioxin when incinerated, and there is a concern that it may have an adverse effect on the environment.

On the other hand, a deposited film of an inorganic oxide such as silicon oxide and aluminum oxide, for example, a deposited film provided by a conventional deposition method using silicon dioxide (SiO ₂ ) as an evaporation source is:
Although transparent, the gas barrier properties are insufficient. Therefore, silicon monoxide (SiO) is used as an evaporation source to form a film in a reaction atmosphere of oxygen, and a silicon oxide film (SiO _x (X
Is less than 1.8). However, the silicon oxide (SiO _x ) exhibits a higher barrier property as X is smaller. However, when X is smaller, there is a problem that the transmittance of visible light is reduced and the film becomes colored. . Further, the inventors of the present invention have already formed SiO _x (1.5 ≦ X ≦
A transparent barrier film having improved barrier properties and transparency by using a thin film mainly composed of 2) has been proposed. (Japanese Patent Application No. 10-188168) However, the oxygen permeability cannot be said to be sufficient even in this barrier film, and improvement is required.

The present invention has been made in view of such circumstances, and has a transparent barrier film having high transparency and high barrier properties, particularly excellent oxygen permeability barrier properties, and a method for producing the same. It is an object of the present invention to provide an apparatus for manufacturing, a laminated material having suitability for post-processing, and a packaging container having good suitability for filling and packaging the contents.

[0007]

In order to achieve the above object, a transparent barrier film of the present invention has at least a base film and a barrier layer provided on at least one surface of the film. In addition, the barrier layer is made of silicon oxide (SiO _Y (1.5%) formed by ion plating using SiO _x (0 ≦ X ≦ 2) as an evaporation source.
≦ Y ≦ 2)) and the oxygen permeability of the thin film is in the range of 0.02 to 0.5 cc / m ² · day.

Further, the transparent barrier film of the present invention has a constitution in which, in addition to the above constitution, the base material is subjected to a heat treatment before forming a barrier layer.

Further, the transparent barrier film of the present invention comprises:
The base film is either a sheet form or a roll winding form, biaxially oriented polypropylene, biaxially oriented polyamide, biaxially oriented polyethylene terephthalate,
The configuration was such that it was any of olefin, styrene-based polymer, cellulose-based polymer, polyalkylene terephthalate, and the like.

In the transparent barrier film of the present invention, the substrate is preliminarily heated when the silicon oxide film is formed, and the heat treatment is performed at a temperature of 40 to 150 ° C.

Further, as a method for producing a transparent barrier film of the present invention, at least a base film and a barrier layer provided on at least one surface of the film, and the barrier layer is formed of SiO _x as an evaporation source (0 ≦ X ≦ 2)
Before forming a barrier layer, the above-described base material is used to form a thin film mainly composed of silicon oxide (SiO _Y (1.5 ≦ Y ≦ 2)) formed by ion plating using A heat-treated manufacturing method was used.

Further, as a method for producing the transparent barrier film of the present invention, the heat treatment is performed at a temperature in the range of 40 to 150 ° C. as the production method. further,
As the method for producing the transparent barrier film of the present invention, the fact that the ion plating method is a holocathode type ion plating method was used as the production method.

Further, as a method for producing the transparent barrier film of the present invention, the base film is in either a sheet form or a roll winding form, and is made of biaxially oriented polypropylene, biaxially oriented polyamide, biaxially oriented polyethylene terephthalate, The production method was a resin film comprising one or a combination of two or more of olefin, styrene-based polymer, cellulose-based polymer, polyalkylene terephthalate, and the like.

Further, the apparatus for producing a transparent barrier film of the present invention comprises:
As a transparent barrier film production apparatus for forming a barrier layer on at least one surface of the substrate film by an ion plating method, a heat treatment unit for pre-heating the substrate in a vacuum,
It was configured to have at least a roll or sheet film transport section and a barrier layer forming section.

Further, in the apparatus for producing a transparent barrier film according to the present invention, the ion plating method is a hollow cathode type ion plating method.

Further, the laminated material of the present invention has a structure in which a heat-sealing resin layer is provided on at least one surface of the transparent barrier film.

Further, the laminated material of the present invention has a structure in which a heat-sealable resin layer is provided on the barrier layer of the above-mentioned transparent barrier film, and a substrate is laminated on a substrate film on which no barrier layer is formed. To be prepared, and
The heat sealing resin layer was provided on the substrate.

Further, the laminate of the present invention comprises an anchor coat agent layer and / or a heat transfer layer between the barrier layer and the heat-sealing resin layer.
Alternatively, a configuration having an adhesive layer was adopted.

The packaging container of the present invention has a configuration in which the above-described laminated material is used to form a bag or a box by heat-sealing a heat-sealing resin layer.

[0020]

The barrier layer made of silicon oxide obtained according to the present invention is a transparent and dense film having excellent oxygen permeation barrier properties and a very high oxygen permeation barrier property, transparency and resistance to a transparent barrier film. Impact properties could be imparted. Further, by using the apparatus for producing a transparent barrier film obtained by such an invention, in particular, by providing a heat treatment section for previously heating the substrate in a vacuum, the barrier property of the substrate, and further provided on the substrate It is possible to improve the barrier characteristics of the barrier film. Furthermore, the laminated material using this transparent barrier film is given post-processing suitability by a heat-sealable resin layer in addition to the above-described respective properties, and the packaging container in which the laminated material is made into a bag or box is excellent in contents. Filling and packaging suitability.

[0021]

Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing one embodiment of the transparent barrier film of the present invention. In FIG. 1, a transparent barrier film 1
Consists of a base film 2 and a barrier layer 3 formed on one surface of the base film 2. In addition, the transparent barrier film of the present invention may have the barrier layer 3 on both sides of the base film 2.

(Base Film) The base film 2 constituting the transparent barrier film 1 of the present invention is a transparent film capable of holding the barrier layer 3, and is deformed, shrunk, etc. by a heat treatment described later. It can be appropriately selected from the purpose of use of the transparent barrier film, except for those that cannot be used as a transparent barrier film. Specifically, as the base film 2, polyolefin resins such as polyethylene, polypropylene, and polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, and ethylene-vinyl acetate copolymers are used. Unified saponified compound,
Polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin,
A stretched (uniaxial or biaxial) or unstretched flexible resin film of a polyester resin, a polyamide resin, or the like can be used. The thickness of the base film 2 is 5
It can be set as appropriate within the range of ５００500 μm.

The present invention is characterized in that the base film is subjected to a heat treatment before forming a barrier layer on the base film. This heat treatment is not restricted by time before the barrier film is formed. For example, heat treatment can be performed in advance before setting the base material in the barrier film forming apparatus, or heat treatment can be performed in the barrier film forming apparatus under normal pressure or under vacuum.

As the heating method, when the heating is performed outside the barrier film forming apparatus, oven heating by ordinary electric resistance heating,
Various methods such as heating in a vacuum oven, heating using hot water, heating using an infrared heater, and heating using ultrasonic vibration can be used, and the method is not limited to these methods.

On the other hand, when the heat treatment in a barrier film production apparatus, but is preferably performed under vacuum, apparatus is dry or N _2, an inert gas atmosphere such as Ar gas, or substituted with those For example, under normal pressure. As the heating method, a radiant heating method using an IR heater, a method in which a film roll axis or a jig during a traveling process is electrically heated by directly contacting the film, and a method of partially heating a base film by a heating method using high-frequency heating or the like are used. Heating can be performed. Alternatively, the inside of the vacuum chamber is heated by electric heating or the like, the entire chamber atmosphere is heated, and each substrate film roll is heated, or a room for pre-heating treatment is provided in the vacuum chamber, and the substrate film is previously set in this room. It can be performed by a method of performing each heating or partial heating of the roll, but is not limited to these methods.

FIG. 2 shows a specific embodiment. The substrate film is subjected to radiant heating by an IR lamp 116, and the state of the heating temperature is monitored by temperature sensors 117a and 117b. More specifically, these two temperature sensors sense the temperature near the surface of the base film roll and the temperature inside the base film roll, and can control the temperature of the entire roll. Although these temperature sensors are not shown, more accurate temperature control can be performed by installing them on both the unwinding roll and the winding roll.

The temperature of the heat treatment is in the range of 40 to 150 ° C., particularly preferably in the range of 60 to 150 ° C. If the temperature is lower than 40 ° C., the degassing of the base film, particularly the PET film, is not sufficiently performed, which is not preferable.
On the other hand, when the temperature is 150 ° C. or more, the base film, particularly the PET film is deformed, which is not preferable from the viewpoint of shape maintenance. Further, the time of the heat treatment is not particularly limited, but it is preferable to perform the heat treatment until the base film is sufficiently degassed (particularly, H ₂ O gas). For example, 1 × 1
It can be sufficiently achieved at 60 ° C. for 1 hour in a vacuum state of 0 ^-4 to 10 ^-5 Torr, but the heating time is reduced by raising the temperature in consideration of the balance with the thermal deformation of the base film. Is possible.

The reason why the performance of the barrier film and the barrier film is improved by the heat treatment of the substrate is not necessarily clear, but the following may be considered. That is, it is considered that radiant heat from the evaporation source during the formation of the barrier layer, or energy is applied to the base film by ion bombardment in plasma or the like, and the surface temperature of the base film is increased. (especially deposition surface vicinity of the substrate film) containing gas, particularly H ₂ O is released, considered that time is released, or the barrier layer is not easily adhere, such as silicon oxide film on the site Can be Therefore, as a result of the formation of the barrier layer, the site becomes defective, and gas such as oxygen easily permeates, and it is considered that the barrier property is reduced. Therefore,
It is considered that these problems could be solved by performing the above-described heat treatment of the base film before film formation.

Further, the base film 2 as described above is required.
If necessary, apply an anchor coat agent to the surface
Surface smoothing processing or the like may be performed. (Barrier Layer) Constituting the Transparent Barrier Film 1 of the Present Invention
Barrier layer 3 is made of SiO 2 as an evaporation source. _X(0 ≦ X ≦ 2)
Oxide deposited by ion-plating method
Element (SiO_Y(1.5 ≦ Y ≦ 2))
Layer. The oxygen content of the silicon oxide thin film is in the above range.
If it is less than, the absorption coefficient of the thin film in visible light increases.
And transparency cannot be ensured. Also, silicon oxide
In addition to the main components of the film, silicon and oxygen,
Minium, magnesium, calcium, potassium, nato
Metals such as lium, titanium, zirconium and yttrium
And non-metallic elements such as carbon, boron, nitrogen and fluorine
It does not matter. Incidentally, the barrier layer 3 is formed of a silicon oxide thin film.
Alternatively, metal aluminum, aluminum oxide
Acid deposited by ion plating using chromium
Consisting of a thin film mainly composed of aluminum oxide thin film AlOx
It may be a layer.

The thickness of the silicon oxide thin film which is the barrier layer 3 of the transparent barrier film 1
Can be arbitrarily selected and set in the range of, for example, about 50 to 3000, preferably about 100 to 1000. The thus obtained transparent barrier film has an oxygen permeability of 0.02 to 0.5.
A range of 5 cc / m 2 · day can be achieved. When the oxygen permeability exceeds 0.5 cc / m2 · day or more, it functions as a normal barrier layer, but is more insufficient for oxygen contamination. For example, it is insufficient for fresh foods, medical drugs, medical instruments, and the like. If not more than 0.02 cc / m 2 · day, the above problem can be solved, but it takes time to prepare the barrier layer and further increases the cost, which is not preferable considering practicality. In the present invention, a surface treatment such as a corona treatment, a plasma treatment, or a silane coupling treatment may be performed on the barrier layer 3 made of the silicon oxide thin film as described above for the purpose of improving post-processing suitability. .

Next, a method of forming the barrier layer 3 on the substrate fill 2 will be described. In the present invention, the barrier layer 3 made of a silicon oxide thin film (SiO _Y (1.5 ≦ Y ≦ 2))
Is formed by using a hollow cathode type ion plating method, a DC type ion plating method, an RF type ion plating method, or the like using SiO _x (0 ≦ X ≦ 2) as an evaporation source. For example, formation of a silicon oxide thin film on the base film 2 by a hollow cathode (HCD) type ion plating method includes mounting an evaporation source SiO _x (0 ≦ X ≦ 2) on a hearth in a chamber, maintaining the pressure in the chamber to about 10 ^-4 Torr, with evaporating SiO _X from the hearth by irradiating the HCD type plasma gun of the plasma flow to the evaporation source, the evaporation molecules by high density plasma generated in the vicinity of the hearth Ionization with high ionization efficiency, forming a thin film of silicon oxide on the base film 2,
The barrier layer 3 can be used. Note that the ion collision effect on the substrate can be obtained with a slight potential difference between the floating potential of the plasma and the sheath potential near the substrate without applying a bias voltage to the substrate.

When the amount of oxygen in SiO _{x as} the evaporation source is insufficient (0 ≦ X ≦ 1.5), a thin film of silicon oxide is formed on the base film 2 while introducing oxygen gas into the chamber. To form a barrier layer 3. FIG. 2 is a configuration diagram of a take-up type hollow cathode (HCD) ion plating apparatus according to an embodiment of the present invention. In Figure 2,
The HCD-type ion plating apparatus 101 is disposed below the coating drum 104, a vacuum chamber 102, a take-up roll 103 a, a supply roll 103 b, a coating drum 104, a partition plate 105 provided in the chamber 102. Anode (hearth) 106,
The plasma gun 107 and the cathode 10 disposed at predetermined positions of the vacuum chamber 2 (the left side wall of the vacuum chamber in the illustrated example).
8, an intermediate electrode 109 and an auxiliary coil 110 are provided. Further, a permanent magnet 111 is provided below the anode 106. Further, the take-up roll 103a and the supply roll 103b are equipped with a reverse mechanism (not shown), and can be unwound and wound in both directions.
This can be used when the preheating treatment of the base film is different from the production speed of the barrier layer. For example, the base film roll is once wound up while performing a pre-heating process, and then the conveyance of the film is reversed, and a barrier layer such as silicon oxide is formed on the heat-treated base film roll by the present apparatus. A film can be formed. Of course, it is needless to say that the base film can be heat-treated to continuously form the barrier layer.

The formation of a silicon oxide thin film using such an HCD type ion plating apparatus 101 is performed as follows. First, an evaporation source 115 is provided on the anode 106,
The pressure inside the vacuum chamber 102 is set to 1 × 10 ⁻⁴ Torr
Do the following. In this state, a plasma gas such as an argon gas (Ar) is introduced into the plasma gun 107. And
The plasma beam 120 generated by the plasma gun 107 is drawn into the vacuum chamber 102 by the magnetic field formed by the auxiliary coil 110, and converges on the evaporation source 115 by the magnetic field generated by the permanent magnet 111 below the anode 106.
This evaporation source 115 is heated. As a result, the evaporation source 115 in the heated portion evaporates, and the evaporated molecules are converted to the anode (hearth).
Ionized by the high-density plasma 120 existing near 106 and collides with the base film 2 moving on the coating drum 104, a thin film of silicon oxide is formed. By winding the base film 2 on which the silicon oxide thin film is formed on a winding roll 103a,
A transparent barrier film having a barrier layer composed of a silicon oxide thin film according to the present invention can be manufactured. Note that a thin film of silicon oxide may be formed in the vacuum chamber 102 while blowing oxygen or the like from an oxygen blowing port (not shown) as needed.

Next, the laminated material of the present invention will be described with reference to an example using the above-described transparent barrier film 1 of the present invention. FIG.
It is an outline sectional view showing an embodiment of a laminated material of the present invention. In FIG. 3, a laminated material 11 includes a transparent barrier film 1 having a barrier layer 3 on one surface of a base film 2, and an anchor coat agent layer and / or an adhesive on the barrier layer 3 of the transparent barrier film 1. A heat-sealing resin layer 13 formed through the layer 12.

The anchor coating agent layer 12 constituting the laminated material 11 is made of, for example, an organic titanium anchor coating agent such as alkyl titanate, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, or the like. Can be formed. The anchor coating agent layer 12 is formed by coating the above-mentioned anchor coating agent with a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and drying the solvent, diluent and the like. It can be done by removing. The coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

The adhesive layer 12 constituting the laminated material 11
For example, polyurethane-based, polyester-based, polyamide-based, epoxy-based, poly (meth) acryl-based, polyvinyl acetate-based, polyolefin-based, casein, wax,
Formed using various types of laminating adhesives such as a solvent type, an aqueous type, a non-solvent type, or a hot-melt type which mainly contains a vehicle such as an ethylene- (meth) acrylic acid copolymer or polybutadiene. Can be. The adhesive layer 12 is formed by coating the above-mentioned laminating adhesive by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and drying the solvent, diluent, and the like. It can be done by removing. As the application amount of the above laminating adhesive,
It is preferably about 0.1 to 5 g / m ² (dry state).

Examples of the heat-sealing resin used for the heat-sealing resin layer 13 constituting the laminated material 11 include resins that can be melted by heat and fused to each other. Specifically, 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 Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as an acid, fumaric acid, itaconic acid or the like, a vinyl acetate resin, a poly (meth) acrylic resin, a polyvinyl chloride resin or the like can be used. The heat-sealing resin layer 13 may be formed by applying the above-described heat-sealing resin, or may be formed by laminating a film or sheet made of the above-described heat-sealing resin. The thickness of such a heat-sealing resin layer 13 can be set within a range of 5 to 300 μm, preferably 10 to 100 μm.

FIG. 4 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 4, the laminated material 21 is:
A transparent barrier film 1 having a barrier layer 3 on one surface of a base film 2, and an anchor coat agent layer and / or an adhesive layer 2 on the barrier layer 3 of the transparent barrier film 1.
2 and a substrate 24 provided on the other surface (the surface on which the barrier layer is not formed) of the substrate film 2 of the transparent barrier film 1. Anchor coating agent layer and adhesive layer 2 constituting laminated material 21
2, and the heat-sealable resin layer 23 can be the same as the anchor coat agent layer, the adhesive layer 12, and the heat-sealable resin layer 13 constituting the above-described laminated material 11, and the description thereof is omitted. I do.

As the base material 24 constituting the laminated material 21,
For example, when the laminated material 21 forms a packaging container, since the base material 34 is a base material, the base material 34 has excellent properties in mechanical, physical, chemical, etc., and particularly has strength. It is possible to use a resin film or sheet which is strong and tough and has heat resistance. Specifically, polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin,
Examples include stretched (uniaxial or biaxial) or unstretched films or sheets of tough resins such as polystyrene resins, polyacetal resins, and fluorine resins. The thickness of the substrate 24 is 5 to 100 μm, preferably 10 to 100 μm.
~ 50 μm is preferred.

Further, in the present invention, even if a desired print pattern such as a character, a figure, a symbol, a picture, a pattern, etc. is printed on the base material 24 by a normal printing method, the front print or the back print is performed. good. Such characters and the like can be recognized very well through the transparent barrier film 1 because the transparent barrier film 1 constituting the laminated material 21 has excellent transparency. Furthermore, in the present invention, for example, various paper base materials constituting a paper layer can be used as the base material 24. Specifically, it is a paper base material having shapeability, bending resistance, rigidity and the like. For example, paper base materials such as pure white roll paper, kraft paper, paperboard, and processed paper can be used.
Such a paper substrate has a basis weight of about 80 to 600 g / m ^2.
Degree is preferable, and more preferably 100 to 4
It is desirable to use a material of about 50 g / m ² . Further, in the present invention, as the substrate 24, the above-mentioned resin film or sheet and the above-mentioned paper substrate can be used in combination.

FIG. 5 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 5, the laminated material 31 is
A transparent barrier film 1 having a barrier layer 3 on one surface of a base film 2, and an anchor coat agent layer and / or an adhesive layer 3 on the barrier layer 3 of the transparent barrier film 1.
2, a heat-sealable resin layer 33 formed via the base material 2, a base material 34 provided on the other surface (the surface on which the barrier layer is not formed) of the base material film 2 of the transparent barrier film 1, and a base material 34 formed on the base material 34. And a heat-sealing resin layer 35. Anchor coat agent layer and adhesive layer 3 constituting laminated material 31
2, and the heat-sealable resin layers 33 and 35 are the anchor coat agent layer and the adhesive layer 12 that constitute the laminated material 11 described above.
And the heat-sealable resin layer 13, and the base material 34 constituting the laminated material 31 can be the same as the base material 24 constituting the above-described laminated material 21. Is omitted.

The laminated material of the present invention further includes, for example,
Water vapor, low-density polyethylene with barrier properties such as water,
Medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, resin films or sheets such as ethylene-propylene copolymer, coloring agents such as resin pigments, and other additives, and kneading. Films or sheets of various colorants having a light-shielding property formed into a film can be used. These materials can be used alone or in combination of two or more, and the thickness is arbitrary, but usually 5 to 300 μm,
Preferably it is about 10 to 100 μm.

Further, when the laminated material of the present invention is used for the purpose of a packaging container, the packaging container is usually exposed to severe physical and chemical conditions. Suitability is required. Intellectually, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability,
Various conditions such as quality maintainability, workability, hygiene, etc. are required. For this reason, the laminated material of the present invention may be arbitrarily selected from materials satisfying the above-described various conditions, It can be used as the film 1, the substrates 24, 34, or other components. Specifically, 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, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, vinyl chloride-vinylidene chloride resin, polystyrene resin, acrylonitrile -Styrene copolymer (A
(BS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitro resin Any known film or sheet of a known resin such as cellulose can be used. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used.

The above film or sheet is unstretched,
Any of those uniaxially or biaxially stretched can be used. The thickness can be arbitrarily determined, but can be selected from a range of several μm to 300 μm. The lamination position is not particularly limited. In the present invention, the sheet without a film may be a film having any property such as extrusion film formation, inflation film formation, and coating. The above-described laminated materials 11, 21, 31
The laminated material of the present invention is a method of laminating a usual packaging material, 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, a co-extrusion inflation method and the like.

When performing the above-mentioned lamination, if necessary,
For example, the film can be subjected to a pretreatment such as a corona treatment or an ozone treatment. For example, isocyanate (urethane) polyethyleneimine, polybutadiene, organotitanium, anchor coating agent, or polyurethane, polyacrylic A known adhesive such as a laminating adhesive of a polyester, polyester, epoxy, polyvinyl acetate or cellulose type can be used.

Next, the packaging container of the present invention will be described. The packaging container of the present invention is a bag or box made by heat fusion using the laminated material of the present invention. Specifically, when the packaging container is a soft packaging bag, the heat-sealing resin layer of the laminated material of the present invention may be folded with the surfaces of the resin layers facing each other, or two laminated materials of the present invention may be laminated, The peripheral end, for example, side seal type, two-side seal type, three-side seal type, four-side seal type,
Envelope seal type, Gassho seal type (pillow seal type), fold seal type, flat bottom seal type, square bottom seal type,
Various forms of packaging containers according to the present invention can be manufactured by forming a sealed portion by heat fusion using other heat sealing forms.

In the above description, heat fusion can be performed by a known method such as a bar seal, a rotating roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal. FIG. 6 is a perspective view showing one embodiment of the packaging container of the present invention as described above. In FIG. 6, a packaging container 51 is formed by stacking a pair of laminated materials 11 of the present invention such that the heat-sealable resin layer 13 faces each other.
In this state, heat sealing is performed on three sides of the peripheral portion to form the seal portion 52. This packaging container 51
The contents can be filled from the opening 53 formed in the other one of the peripheral portions. In addition to the above, the packaging container of the present invention is, for example, a self-supporting packaging bag (standing pouch).
And the like, and a tube container or the like can be manufactured using the laminated material of the present invention.

In the present invention, for example, a one-piece type, a two-piece type, another inlet, or a zipper for opening and closing can be arbitrarily attached to the above-mentioned packaging container. Further, when the packaging container of the present invention is a liquid-filled paper container containing a paper substrate, a blank plate for manufacturing a desired paper container is produced using the laminated material of the present invention in which the paper substrates are laminated. By using this blank plate to form the trunk, bottom, head, etc., for example,
Brick type, flat type or Gebelt type liquid paper containers can be manufactured. In addition, the shape thereof can be manufactured by any of a square container, a cylindrical paper can such as a round shape, and the like.

FIG. 7 is a perspective view showing one embodiment of the above-mentioned liquid-filled paper container which is a packaging container of the present invention.
FIG. 8 is a plan view of a blank plate used for the packaging container shown in FIG. The blank plate 70 uses, for example, the laminated material 31 of the present invention shown in FIG. 5, and press lines m, m... For bending in forming a container, and a trunk forming the trunk 62 of the container 61. Panels 71, 72, 73, 74
And a top panel 71a constituting a top 63 of the container 61,
72a, 73a, 74a, and bottom panels 71b, 72b, 73b, 74b constituting the bottom 64 of the container 61;
It is manufactured by punching so as to include a heat-sealing panel 75 for forming a cylindrical body. This blank plate 7
0 is bent by pressing lines m, m,.
And the outside of the heat-sealing panel 75 is heat-sealed to form a tubular body, and then the bottom panels 71b, 72b, 7
3b, 74b are bent by pressing lines m, m,... And are heat-sealed and filled with liquid from the top opening.
By folding and heat-sealing 1a, 72a, 73a, 74a along the pressing lines m, m,..., A packaging container 61 filled with liquid can be obtained.

The packaging container of the present invention is used for filling and packaging various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other various articles. It is.

[0051]

Next, the present invention will be described in more detail with reference to examples. (Example 1) A roll-shaped biaxially stretched polyethylene terephthalate film (Tray Co., Ltd.
-60, thickness 12μm, width 660mm, length 5000
m) and mounted in a chamber of a take-up horocathode ion plating apparatus as shown in FIG. Next, the inside of the chamber was reached at a degree of ultimate vacuum of 1 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump.
The pressure was reduced to Subsequently, the rolled film shown in FIG.
At a rate of 60 ° C./min, heating was performed at 60 ° C. by the IR heater 116 before forming the barrier layer. At this time, the degree of vacuum was 1 × 10 ⁻⁴ Torr. Next, the pressure in the chamber was reduced to an ultimate vacuum of 1 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump.

Silicon dioxide (manufactured by Merck Japan KK, purity: 99%, particle size: 2.5 to 4 mm) was prepared as an evaporation source and mounted on an anode (hearth). By controlling the opening / closing degree of a valve between the vacuum pump and the chamber, the pressure in the chamber during film formation is increased to 1 × 10 ⁻³ Torr.
Using a hollow cathode type plasma gun introduced with argon gas, the plasma flow is evaporated by converging and irradiating the plasma flow to an evaporation source on the anode (hearth) while unwinding the roll that has been subjected to the heat treatment of the base film while maintaining the temperature. Evaporated molecules were ionized by high-density plasma to form a thin film of silicon oxide (SiOy (y = 1.9)) on the base film. The traveling speed of the base film is set to 100 m so that the thickness of the formed silicon oxide layer becomes 20 nm.
/ Min.

In forming silicon oxide on the substrate film, the substrate film was cooled to -10 ° C. in order to reduce thermal damage of the substrate film due to the plasma ion flow. Specifically, -10 is formed in the film forming drum 104 (FIG. 2).
The temperature of the drum was lowered by flowing an ethylene glycol refrigerant cooled to ° C., and the substrate film was cooled. The thickness of the silicon oxide thin film was measured using a fluorescent X-ray analyzer (RIX-3100 manufactured by Rigaku Corporation). Thus, a transparent barrier film (Sample 1) of the present invention was obtained.

Example 2 A transparent barrier film of the present invention (Sample 2) was prepared in the same manner as in Example 1 except that the heat treatment before forming the thin film was performed at 100 ° C. and 30 m / min with an IR heater. I got (Example 3) A transparent barrier film (sample 3) of the present invention was obtained by performing the same operation as in Example 1 except that the heat treatment before forming the thin film was performed at 120 ° C and 50 m / min with an IR heater. . (Example 4) Winding of base film, IR lamp 116
Then, the same operation as in Example 1 was performed except that the silicon oxide barrier layer was continuously formed at a rate of 30 m / min while performing the heat treatment at 60 ° C., and the transparent barrier film of the present invention (sample 4) I got (Example 5) The base film take-up roll was stopped,
In this state, heat treatment was performed at 60 ° C. for 1 hour with the IR lamp 116, and then the heating unit was moved to the film forming drum 104, and a barrier layer was formed in the heated part of the base film in that state. The same operation as in Example 1 was performed to obtain a transparent barrier film of the present invention (Sample 5).

Example 6 A roll-shaped biaxially stretched polyethylene terephthalate film (Lumirror S-10 manufactured by Toray Industries, Ltd., thickness 12 μm, width 600) was used as a base film.
mm and a length of 5000 m), and this was mounted in a chamber of a take-up type hollow cathode ion plating apparatus as shown in FIG. Next, the pressure in the chamber was reduced to an ultimate vacuum of 1 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump. Silicon dioxide (purity 99%, particle size 2.5 to 4 mm, manufactured by Merck Japan Ltd.) was prepared as an evaporation source and mounted on an anode (hearth). Next, while winding the roll film, a high frequency of 13.56 MHz was applied to an electrode (not shown) facing the film at a stage before the thin film was formed, and the base film was instantaneously heated to 70 ° C. .

Next, oxygen gas was introduced at a flow rate of 50 sccm near the coating drum of the chamber, and the opening / closing degree of a valve between the vacuum pump and the chamber was controlled to reduce the pressure in the chamber during film formation. 1 × 10 ^-3
Torr. Then, using a holo-cathode type plasma gun into which argon gas is introduced, the plasma flow is converged and irradiated to the evaporation source on the anode (hearth) to evaporate, and the evaporated molecules are ionized by high-density plasma, and the base film is formed. Silicon oxide (SiOy (y = 1.
9)) A thin film was formed. The running speed of the substrate film was set to 100 m / min so that the thickness of the formed silicon oxide layer became 20 nm.

In forming silicon oxide on the substrate film, the substrate film was cooled to -10 ° C. in order to reduce the thermal damage of the substrate film due to the plasma ion flow. Specifically, -10 is formed in the film forming drum 104 (FIG. 2).
The temperature of the drum was lowered by flowing an ethylene glycol refrigerant cooled to ° C., and the substrate film was cooled. The thickness of the silicon oxide thin film was measured using a fluorescent X-ray analyzer (RIX-3100 manufactured by Rigaku Corporation). Thus, a transparent barrier film of the present invention (sample 6) was obtained.

(Comparative Example) In the thin film manufacturing method of Example 1, a silicon oxide film was manufactured without performing heat treatment on the roll film. (Evaluation) The oxygen transmittance of the silicon oxide thin films of the various transparent barrier films produced as described above was measured as follows, and the results are shown in Table 1.

Oxygen Permeability Using a MOCON type gas permeability measuring device (OXTRAN 2/20 manufactured by Modern Control), the oxygen permeability was measured at a temperature of 23 ° C. and a humidity of 0% RH. Water vapor transmission rate Water vapor transmission rate measuring device (PER manufactured by Modern Control Co., Ltd.)
MATRAN-W3 / 31) at a temperature of 38 ° C. and a humidity of 100% RH. Using an adhesive consisting of a 7% solution of a two-component curable polyurethane resin suitable for post-processing and filling and packaging , an adhesive layer (1 μm thick) was formed on the silicon oxide thin film of each of the prepared barrier films. Next, a low-density polyethylene was extrusion-coated on the adhesive layer to form a heat-sealable resin layer having a thickness of 60 μm.
A laminated material having a layer configuration as shown in FIG. 3 was produced. Next, using each laminated material, a three-side sealed plastic bag as shown in FIG. 6 is manufactured by a bag making machine, and after filling the plastic bag with soy sauce, the opening is thermally melted. To produce a filled packaging product. The suitability in this series of processing was evaluated based on the following criteria, and the result was regarded as suitability for post-processing and suitability for filling and packaging.

(Evaluation Criteria) な く: No defects in appearance, no alteration of contents after several days in a general environment, and freshness was maintained. X: Defects appeared on the appearance, or the contents deteriorated remarkably after several days in a normal environment.

[0061]

[Table 1]

As shown in Table 1, it was confirmed that all of the transparent barrier films (samples 1 to 4) of the present invention had excellent oxygen permeation barrier properties, and were suitable for post-processing and filling and packaging. Was done. On the other hand, although the comparative sample has relatively good oxygen permeability barrier properties as the conventional type, there is a difference as compared with the transparent barrier film of the present invention, the barrier layer properties are inferior, and the suitability for post-processing and filling and packaging is also good. It was not enough.

Measurement of Degassing of Base Film FIG. 9 shows an example of a biaxially stretched polyethylene terephthalate film (PET film) (T-6 manufactured by Toray Industries, Inc.).
0 and a thickness of 12 μm) in the apparatus shown in FIG. 2 in a steady heating state at 60 ° C., using a degassing mass spectrometer (TDS-2000 manufactured by ULVAC, Inc.). As is clear from FIG. 9 and FIG. 9, OH ⁺ having a mass number of 17 and H ₂ O ⁺ having a mass number of 18 were remarkably observed in the same base film, and H ₂ ^{+ having} a mass number of 2 and CO 2 having a mass number of 28 were observed. ⁺ ,
CO ₂ ^{+ with} a mass number of 44 was observed. As a result, PET
In the heat treatment of the base film, the degassing of water occurs most frequently, and it is considered that the degassing of water occurs at the time of forming the barrier layer, thereby deteriorating the barrier performance.

[0064]

As described above in _{detail, SiO X (0 ≦ X ≦} 2) silicon oxide deposited by an ion pre-plating method using the evaporation source according to the present invention (SiO _Y (1.
The barrier layer composed of 5 ≦ Y ≦ 2) has an excellent oxygen permeation barrier property and a good transparency, is dense and has a high oxygen permeation barrier property by being subjected to a specific heat treatment before film formation. Since it has impact resistance, the transparent barrier film provided with such a barrier layer can stably maintain a high oxygen permeation barrier property. Further, in addition to the above properties, the laminated material using the transparent barrier film has post-processing suitability with a heat-sealable resin layer. It has excellent suitability for filling and packaging the contents and has good suitability for microwave ovens.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a transparent barrier film of the present invention.

FIG. 2 is a specific explanatory view of a holo-cathode ion plating apparatus used for producing the transparent barrier film of the present invention.

FIG. 3 is a schematic sectional view showing an embodiment of a laminated material using the transparent barrier film of the present invention.

FIG. 4 is a schematic sectional view showing another embodiment of a laminated material using the transparent barrier film of the present invention.

FIG. 5 is a schematic cross-sectional view showing another embodiment of the laminated material using the transparent barrier film of the present invention.

FIG. 6 is a schematic sectional view showing an embodiment of a packaging container using the transparent barrier film of the present invention.

FIG. 7 is a schematic sectional view showing another embodiment of a packaging container using the transparent barrier film of the present invention.

FIG. 8 is a plan view of a blank plate used for manufacturing the packaging container shown in FIG.

FIG. 9 is a diagram showing one measurement result obtained by performing mass spectrometry of degassing when the base film of the present invention is subjected to preheating treatment.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Transparent barrier film 2 Base film 3 Barrier layer 11, 21, 31 Laminated material 12, 22, 32 Anchor coating agent layer, adhesive layer 13, 23, 33 Heat-sealable resin layer 51, 61 Packaging container 101 Holo cathode type Ion plating apparatus 102 Vacuum chamber 104 Coating drum 107 Hollow cathode plasma gun 115 Raw material 116 IR lamp 117a, b Temperature sensor 118 RF power supply 119 Ar gas introduction pipe

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) B65D 30/02 B65D 30/02 65/40 65/40 DF term (reference) 3E064 AA01 BA30 BA36 BA55 BB10 BC08 BC13 3E086 AD01 AD02 BA04 BA15 BA24 BA40 BB02 BB05 BB15 BB22 BB85 CA01 CA28 4F100 AA20B AA20C AJ04A AK01D AK01E AK03A AK07A AK12A AK42 J AK46A AR00B AR00C AT00A BA02 BA03 BA10 BA05 BA10 BA05 BA10 JL12D JL12E JM02B JM02C JN01

Claims (16)

[Claims] 2. The method according to claim 1, further comprising a base film, and a barrier layer provided on at least one surface of the film, wherein the barrier layer is formed of SiO _x (0 ≦ X) as an evaporation source.
≦ 2), a thin film mainly composed of silicon oxide (SiO _Y (1.5 ≦ Y ≦ 2)) formed by an ion plating method, and having an oxygen permeability of 0.02 to
A transparent barrier film having a range of 0.5 cc / m ² · day. 2. It has at least a substrate film and a barrier layer provided on at least one surface of the film, wherein the substrate is heat-treated before forming a barrier layer, and The barrier layer is made of SiO 2 as an evaporation source.
Silicon oxide (SiO _Y (1.5 ≦ Y ≦ 2)) formed by ion plating using _X (0 ≦ X ≦ 2)
The transparent barrier film according to claim 1, which is a thin film mainly composed of: 3. The transparent barrier film according to claim 1, wherein the heat treatment is performed at a temperature in the range of 40 to 150 ° C. 4. The base film is in either a sheet form or a roll winding form, and is made of biaxially oriented polypropylene, biaxially oriented polyamide, biaxially oriented polyethylene terephthalate, olefin, styrene-based polymer,
The transparent barrier film according to any one of claims 1 to 3, wherein the transparent barrier film is a resin film composed of one or a combination of two or more of a cellulosic polymer and polyalkylene terephthalate. 5. It has at least a base film and a barrier layer provided on at least one surface of the film, wherein the base material has been subjected to a heat treatment before forming a barrier layer, and The barrier layer is made of SiO 2 as an evaporation source.
Silicon oxide (SiO _Y (1.5 ≦ Y ≦ 2)) formed by ion plating using _X (0 ≦ X ≦ 2)
A method for producing a transparent barrier film, comprising a thin film mainly composed of: 6. The method according to claim 5, wherein the heat treatment is performed at a temperature in the range of 40 to 150 ° C. 7. The method for producing a transparent barrier film according to claim 5, wherein the ion plating method is a holocathode type ion plating method. 8. The base film may be in a sheet form or a roll-wound form, and may be biaxially oriented polypropylene, biaxially oriented polyamide, biaxially oriented polyethylene terephthalate, olefin, styrene-based polymer,
The method for producing a transparent barrier film according to any one of claims 5 to 7, wherein the resin film is a resin film made of one or a combination of two or more of a cellulosic polymer and polyalkylene terephthalate. 9. A transparent barrier film forming apparatus for forming a barrier layer on at least one surface of a substrate film by an ion plating method, wherein the substrate is heated in a vacuum in advance, or a roll or sheet. Wherein at least the film transport section and the barrier layer forming section are provided. 10. The apparatus according to claim 9, wherein the ion plating method is a hollow cathode ion plating method. 11. A laminate comprising a transparent barrier film according to claim 1 and a heat-sealing resin layer provided on at least one surface of the transparent barrier film. 12. A laminated material comprising a heat-sealing resin layer provided on a barrier layer of the transparent barrier film according to claim 1. Description: 13. The laminated material according to claim 12, wherein a base material is laminated on a base film on which no barrier layer is formed. 14. The laminated material according to claim 13, further comprising a heat-sealing resin layer on the base material. 15. The laminate according to claim 11, further comprising an anchor coat agent layer and / or an adhesive layer between the barrier layer and the heat-sealing resin layer. 16. A packaging container obtained by using the laminated material according to claim 11 and heat-sealing a heat-sealing resin layer to form a bag or a box.