JP2000006302A - Transparent barrier film, and laminated material and packaging container using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve transparency and barrier properties by providing a barrier layer on one side of a base film, which is composed of a thin film having a silicon oxide as a main component formed by ion plating using SiOx as an evaporation source. SOLUTION: A base film 2 is composed by using an oriented or an unoriented flexible resin film selected from a polyolefin resin such as a polyethylene, a polypropylene, a polybutene or the like, a (meth)acrylic resin, a polyvinyl chloride resin, a polystyrene resin, a polyvinylidene chloride resin and the like. A barrier layer 3, which is composed of a thin film having a silicon oxide, SiOy (1.5<=y<=2) as a main component and composed by ion plating using SiOx (0<=x<=2) as an evaporation source, is formed on one side of the base film 2. Thereby, transparency is excellent, cracks do not generate by bending or the like, and high barrier properties can be securely maintained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent barrier film, a laminated material and a packaging container using the same, and more particularly to a transparent barrier film having excellent barrier properties, transparency and impact resistance, and excellent storage suitability. And a laminate and packaging container having microwave oven suitability and post-processing suitability.

[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 and pharmaceuticals. , A transparent barrier film comprising 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 A transparent barrier film having a configuration in which an inorganic oxide vapor-deposited film is provided, and a packaging laminate and a packaging container using the same have been proposed.

[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.

[0004]

However, among the above-mentioned transparent barrier films and packaging laminates using the same, among the above-mentioned transparent barrier films provided with a coating layer of polyvinylidene chloride or an ethylene vinyl alcohol copolymer, In addition, there is a problem that the barrier properties against oxygen and water vapor are not sufficient, and the barrier properties are significantly reduced particularly in sterilization treatment at a high temperature. Furthermore, a transparent barrier film provided with a coating layer of polyvinylidene chloride
Poisonous dioxins are generated during incineration, and there is a concern that it will have a negative impact on the environment.

On the other hand, a vapor deposited film of an inorganic oxide such as silicon oxide or aluminum oxide, for example, a vapor deposited film provided by a conventional vapor deposition method using silicon dioxide (SiO ₂ ) as an evaporation source is transparent but has a gas barrier property. Not enough. Therefore, silicon monoxide (SiO) is used as an evaporation source to form a film in a reactive atmosphere of oxygen to form a silicon oxide film (SiO _x (x is 1.8 or less)). . However, the silicon oxide film (SiO _x ) exhibits a higher gas barrier property as x is smaller. However, when x is smaller, the transmittance of visible light is reduced, and the film becomes colored. There is.

The present invention has been made in view of such circumstances, and has a transparent barrier film having excellent transparency and high barrier properties, excellent impact resistance, and further suitable for post-processing. It is an object of the present invention to provide a laminated material and a packaging container having good filling and packaging suitability for contents.

[0007]

In order to achieve the above object, a transparent barrier film of the present invention comprises a base film and a barrier layer provided on at least one surface of the base film. The barrier layer is formed of silicon oxide (SiO _y (1.5 ≦ 1.5) formed by ion plating using SiO _x (0 ≦ x ≦ 2) as an evaporation source.
It was configured to be a thin film mainly composed of y ≦ 2)).

Further, in the transparent barrier film of the present invention, the silicon oxide film has a refractive index at a wavelength of 633 nm of 1.4.
The configuration was such that it was in the range of 5 to 1.60.

Further, the transparent barrier film of the present invention has a structure in which the ion plating is a hollow cathode type ion plating.

Further, the transparent barrier film of the present invention comprises:
The base film is a biaxially oriented polypropylene film,
The configuration was such that it was either a biaxially stretched polyamide film or a biaxially stretched polyethylene terephthalate film.

The laminated material of the present invention has such a structure that 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-sealing 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.

In the present invention, the barrier layer made of a silicon oxide film has excellent transparency and is dense, and imparts extremely high transparency, barrier properties and impact resistance to the transparent barrier film. The laminated material using a barrier film is given post-processing suitability by a heat-sealable resin layer in addition to the above-mentioned properties, and the packaging container made from this laminated material in a bag or a box is excellent in filling and packaging of contents. Is provided.

[0016]

Next, an embodiment of the present invention will be described with reference to the drawings. Transparent Barrier Film FIG. 1 is a schematic sectional view showing one embodiment of the transparent barrier film of the present invention. In FIG. 1, the transparent barrier film 1
Comprises 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 comprises barrier layers 3 on both sides of the base film 2.
May be provided. (Base Film) The base film 2 constituting the transparent barrier film 1 of the present invention is not particularly limited as long as it is a transparent film capable of holding the barrier layer 3, and is appropriately selected from the purpose of use of the transparent barrier film and the like. be able to. 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. Stretched (uniaxial or biaxial) or unstretched flexible resin film of unified saponified product, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin, etc. Can be used. The thickness of the base film 2 is 5 to 500 μm, preferably 10 to 500 μm.
It can be set appropriately within the range of 100 μm.

Further, the base film 2 as described above may be, if necessary, coated on its surface with an anchor coating agent or the like and subjected to a surface smoothing treatment or the like. (Barrier Layer) The barrier layer 3 constituting the transparent barrier film 1 of the present invention is formed of silicon oxide (SiO _y (1...) Formed by ion plating using SiO _x (0 ≦ x ≦ 2) as an evaporation source. It is a layer composed of a thin film mainly composed of 5 ≦ y ≦ 2)). If the amount of oxygen in the silicon oxide thin film falls below the above range, the absorption coefficient of the thin film in visible light increases, and the transparency cannot be ensured. Further, in addition to silicon and oxygen, which are main components of the silicon oxide thin film, metals such as aluminum, magnesium, calcium, potassium, sodium, titanium, zirconium, and yttrium, and nonmetallic elements such as carbon, boron, nitrogen, and fluorine May be included. Instead of the silicon oxide thin film, the barrier layer 3 may be a layer composed mainly of an aluminum oxide thin film AlO _{x formed} by ion plating using metal aluminum or aluminum oxide as an evaporation source.

Such a silicon oxide thin film has a wavelength of 633 nm.
The silicon oxide thin film has a refractive index at m in the range of 1.45 to 1.60. The above-mentioned refractive index is obtained by optical measurement, that is, ellipsometry or spectral characteristic measurement. Further, since the refractive index depends on the wavelength of the measuring light, the refractive index in the present invention refers to the refractive index when the wavelength of the measuring light is 633 nm.

Here, the refractive index in the visible light region as described above is determined by the light scattering ability in the target medium. Since light scattering is caused by electrons, the light scattering ability of a certain atom is determined by the number and state of the electrons belonging to the atom, and has a substantially constant value depending on the type of the atom. Therefore, the refractive index of the medium is proportional to the light scattering ability per atom of the atoms contained in the medium and the amount of the atoms that cause light scattering per unit volume. That is, if the number of atoms contained per unit volume is constant, the refractive index is determined by the composition ratio of the atoms (chemical composition of the medium). For example, in the case of silicon and oxygen, since silicon has higher light scattered light, the refractive index increases when the amount of silicon is large and the amount of oxygen is small. Further, if the chemical composition of the medium is constant, the refractive index increases as the number of atoms contained per unit volume increases, that is, as the distance between the atoms becomes shorter and denser.

When the refractive index of the silicon oxide thin film is less than 1.45, as described above, the medium becomes sparse due to the widened atomic spacing, the denseness of the silicon oxide thin film is lost, and the barrier layer 3
However, sufficient barrier properties and impact resistance required can not be secured. Therefore, the higher the refractive index, the better, but as described above, it is difficult to form a silicon oxide thin film having a refractive index exceeding 1.60 even if the denseness is improved while maintaining the chemical composition. It is. Increasing the refractive index further causes a change in the chemical composition, which increases the ratio of silicon to oxygen and decreases the degree of oxidation of silicon. It is not preferable because the absorption coefficient of the thin film with respect to visible light increases and the barrier layer 3 is colored.

The thickness of the silicon oxide thin film which is the barrier layer 3 of the transparent barrier film 1
It varies depending on the type of
It can be arbitrarily selected and set within a range of about {, preferably about 100 to 1000}.

In the present invention, a surface treatment such as a corona treatment, a plasma treatment, a silane coupling treatment or the like is applied to the barrier layer 3 made of a silicon oxide thin film as described above for the purpose of improving post-processing suitability. No problem.

Next, a method of forming the barrier layer 3 on the base film 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 hollow cathode ion plating, DC ion plating, RF ion plating, or the like using SiO _x (0 ≦ x ≦ 2) as the 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 is performed by using SiO _x (0 ≦ x ≦
2) is placed on a hearth in the chamber, and the pressure in the chamber is maintained at several mTorr to several tens mTorr,
The evaporation source is irradiated with a plasma stream from an HCD type plasma gun to evaporate SiO _x from the hearth, and the high-density plasma generated near the hearth ionizes the evaporated molecules at a high ionization rate and oxidizes on the base film 2. The barrier layer 3 can be formed by forming a silicon thin film. still,
Even without applying a bias potential to the substrate, an 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.
If the oxygen amount of 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 shows a winding hollow cathode (HC)
It is a schematic structure figure showing an example of the ion plating device of the D) type. In FIG. 2, the HCD-type ion plating apparatus 101 includes a vacuum chamber 102, a supply roll 103 a, a take-up roll 103 b, a coating drum 104, a partition plate 105, and a lower part of the coating drum 104. An anode (hearth) 106 is provided, a plasma gun 107, a cathode 108, an intermediate electrode 109, and an auxiliary coil 110 provided at a predetermined position (left side wall of the vacuum chamber in the illustrated example) of the vacuum chamber 2. Further, a permanent magnet 111 is provided below the anode 106.

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 arranged on the anode 106,
The pressure inside the vacuum chamber 102 is set to several mTorr to several tens mTorr. In this state, argon (Ar)
Is introduced into the plasma gun 107.
Then, the plasma beam 120 generated by the plasma gun 107 is drawn into the vacuum chamber 102 by a magnetic field formed by the auxiliary coil 110,
The evaporation source 115 is generated by the magnetic field generated by the lower permanent magnet 111.
And the evaporation source 115 is heated. As a result, the heated portion of the evaporation source 115 evaporates, and the evaporated molecules are discharged from the high-density plasma 1 existing near the anode (hearth) 106.
20, it collides with the base film 2 moving on the coating drum 104 to form a thin film of silicon oxide. By winding the base film 2 having the silicon oxide thin film formed thereon in the winding roll 103b, a transparent barrier film having a barrier layer made 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 outlet (not shown) as needed. Laminated Material 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. 3 is a schematic sectional view showing an embodiment of the 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 layer on the barrier layer 3 of the transparent barrier film 1. And a heat-sealable resin layer 13 formed therebetween.

The anchor coating agent layer 12 constituting the laminated material 11 uses, 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 formation of the anchor coat agent layer 12 is performed by coating the above-mentioned anchor coat agent with a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like. Drying and removal can be performed. The coating amount of the above anchor coating agent is 0.1 to 5 g / m.
^{About 2} (dry state) is preferable.

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,
Using various types of laminating adhesives, such as solvent-based, aqueous-based, solvent-free, or hot-melt-based adhesives, whose main components are vehicles such as ethylene- (meth) acrylic acid copolymer and polybutadiene. Can be formed. The adhesive layer 12 is formed by coating the above-mentioned laminating adhesive with, for example, a roll coat, a gravure coat, a knife coat, a deb coat, a spray coat, or another coating method, and drying and removing a solvent, a diluent, and the like. You can do it. The amount of the laminating adhesive applied 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, and itaconic acid, a polyvinyl acetate resin, a poly (meth) acrylic resin, a polyvinyl chloride resin, and the like can be used. The heat-sealable resin layer 13 may be formed by applying the heat-sealable resin as described above, or may be formed by laminating a film or sheet made of the heat-sealable resin as described above. . The thickness of the heat-sealing resin layer 13 is 5 to 300 μm, preferably 10 to 100 μm.
Can be set within the range.

FIG. 4 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 4, a laminated material 21 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 layer on the barrier layer 3 of the transparent barrier film 1. 22
And a base material 24 provided on the other surface (the surface on which the barrier layer is not formed) of the base film 2 of the transparent barrier film 1.

The anchor coat agent layer, the adhesive layer 22 and the heat-sealable resin layer 23 constituting the laminated material 21
It can be the same as the anchor coat agent layer, the adhesive layer 12 and the heat-sealable resin layer 13 that constitute the laminated material 11 described above, and the description is omitted here.

The base material 24 constituting the laminated material 21 includes
For example, when the laminated material 21 forms a packaging container, since the base material 24 is a basic material, it has excellent properties in mechanical, physical, chemical, etc., and particularly has strength. A resin film or sheet which is strong and tough and has heat resistance can be used. Specifically, stretching of strong resin such as polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. (uniaxial or biaxial) Or an unstretched film or sheet can be mentioned. The thickness of the substrate 24 is desirably about 5 to 100 μm, preferably about 10 to 50 μm.

In the present invention, a desired print pattern such as a character, a figure, a symbol, a picture, a pattern, or the like is printed on the base material 24 by a normal printing method. Is also good. Such characters and the like can be visually recognized very well through the transparent barrier film 1 because the transparent barrier film 1 constituting the laminated material 21 has excellent transparency.

Further, in the present invention, as the base material 24, for example, various paper base materials constituting a paper layer can be used. Specifically, it is a paper substrate having shapeability, bending resistance, rigidity, etc., for example, a strong size bleached or unbleached paper substrate, or pure white roll paper, kraft paper, paperboard, processed Paper substrates such as paper can be used. Examples of such paper substrates, of the order of a basis weight of about 80~600g / m ^2, preferably, it is desirable to use of about a basis weight of about 100~450g / m ^2.

In the present invention, as the base material 24, the above-mentioned resin film or sheet and the above-mentioned paper base material 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, a laminated material 31 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 layer on the barrier layer 3 of the transparent barrier film 1. 32
A heat-sealable resin layer 33 formed through the base material, a base material 34 provided on the other surface (non-barrier layer forming surface) 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.

The anchor coat agent layer, the adhesive layer 32 and the heat-sealable resin layers 33, 3 constituting the laminated material 31
5 can be the same as the anchor coat agent layer, the adhesive layer 12 and the heat-sealable resin layer 13 that constitute the laminated material 11 described above, and the base material 34 that constitutes the laminated material 31 is Since it can be the same as the base material 24 constituting the laminated material 21, the description is omitted here.

The laminated material of the present invention further includes, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene having a barrier property against water vapor, water and the like. Resin film or sheet such as copolymer, or resin film or sheet such as polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer having a barrier property against oxygen, water vapor, etc. And various kinds of colored resin films or sheets having a light-shielding property, which are formed by adding a desired colorant and other desired additives and kneading to form a film.

These materials can be used alone or in combination of two or more, and the thickness is optional.
Usually, it is about 5 to 300 μm, preferably about 10 to 100 μm.

Furthermore, when the laminated material of the present invention is used for packaging, the packaging is usually subjected to severe physical and chemical conditions. Packaging suitability is required. Specifically, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability,
Various conditions such as quality preservation, workability, hygiene, etc. are required. For this reason, the laminated material of the present invention is arbitrarily selected from materials satisfying the above-mentioned 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 Polymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene 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, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. can do. 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 is arbitrary,
It can be used by selecting from a range of about several μm to 300 μm, and the lamination position is not particularly limited. In the present invention, the film or sheet is formed by extrusion film formation,
Any film such as an inflation film or a coating film may be used.

The laminated materials of the present invention, such as the laminated materials 11, 21 and 31 described above, can be formed by laminating ordinary packaging materials, for example, wet lamination, dry lamination, solventless dry lamination, extrusion lamination. It can be manufactured using a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, a co-extrusion inflation method or the like.

When performing the above-mentioned lamination, if necessary,
For example, a film can be subjected to a pretreatment such as a corona treatment and an ozone treatment. For example, an anchor coating agent such as an isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or a polyurethane, Known adhesives such as polyacrylic, polyester-based, epoxy-based, polyvinyl acetate-based, and cellulose-based adhesives for lamination can be used. Next, the packaging container of the present invention will be described.

The packaging container of the present invention is formed by making a bag or box 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 thereof facing each other, or two laminated materials of the present invention may be laminated. Together, the peripheral end, for example, a side seal type,
Heat due to heat sealing form such as two-sided seal type, three-sided seal type, four-sided seal type, envelope-attached seal type, gasket-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type and others By fusing to form a seal portion, various types of packaging containers according to the present invention can be manufactured.

In the above, the thermal 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, an ultrasonic seal, and the like.

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 obtained by laminating a set of laminated materials 11 of the present invention so that their heat-sealable resin layers 13 are opposed to each other. Part 5
2 is formed. The packaging container 51 can be filled with contents from an opening 53 formed in the other one of the peripheral portions. Then, after filling the contents, the opening 53 is heat-sealed to form a seal portion, whereby a packaging container filled with the contents can be obtained.

In addition to the above, the packaging container of the present invention can be, for example, a self-supporting packaging bag (standing pouch). Further, a tube container or the like can be produced by using the laminated material of the present invention. Can be.

In the present invention, for example, a one-piece type, a two-piece type, another pouring device, or a zipper for opening and closing can be arbitrarily attached to the above-mentioned packaging container.

When the packaging container of the present invention is a liquid-filled paper container containing a paper substrate, a blank for producing a desired paper container using the laminated material of the present invention in which the paper substrates are laminated. Make a board, using this blank board, trunk, bottom,
By forming the head or the like, for example, a brick type, flat type or Goebel top type liquid paper container or the like can be manufactured. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

FIG. 7 is a perspective view showing an 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 container shown in FIG. FIG. The blank plate 70 uses, for example, the laminated material 31 of the present invention shown in FIG. 5, and includes pressing lines m, m,... For bending in forming the container, and a trunk forming the trunk 62 of the container 61. Panels 71, 72, 73, 74,
Top panels 71a, 72 constituting the top 63 of the container 61
a, 73a, 74a, a bottom panel 71b, 72b, 73b, 74b constituting a bottom 64 of the container 61, and a heat-sealing panel 75 for forming a cylindrical body. is there. This blank plate 70 is bent by pressing lines m, m,..., And the inside of the end of the body panel 71 and the outside of the heat-sealing panel 75 are heat-sealed to form a cylindrical body, and thereafter, the bottom panel 71b , 72b, 73b, 7
4b are bent by pressing lines m, m, and are heat-sealed and filled with liquid from the top opening, and then the top panels 71a, 72
a, 73a, 74a are bent by pressing lines m, m,.
It can be 1.

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

[0053]

Next, the present invention will be described in more detail with reference to examples. Example 1 A roll-shaped biaxially stretched polyethylene terephthalate film (Lumirror S-10 manufactured by Toray Industries, Inc., thickness 12 μm, width 600 mm, length 50) as a base film
00m) was prepared and mounted in a chamber of a roll-up type hollow cathode ion plating apparatus as shown in FIG. Next, the inside of the chamber was reached at an ultimate vacuum of 5 × 10 ⁻⁵ by an oil rotary pump and an oil diffusion pump.
The pressure was reduced to Torr.

Further, silicon dioxide (purity: 99.7%, particle size: 1 to 5 mm, manufactured by Merck Japan Ltd.) was prepared as an evaporation source, and was placed on an anode (hearth).

Next, oxygen gas was introduced at a flow rate of 50 sccm near the coating drum of the chamber, and the degree of opening and closing of a valve between the vacuum pump and the chamber was controlled to reduce the pressure in the chamber during film formation. 2 × 10 ^-3
Torr. Then, using a hollow cathode type plasma gun into which argon gas has been introduced, the plasma flow is converged and irradiated to an evaporation source on the anode (hearth) to evaporate, and the vaporized molecules are ionized by high-density plasma, and the base material is ionized. Silicon oxide (SiO _y (y = 1.
9)) A thin film was formed. The traveling speed of the base film is
100 m / m so that the thickness of the silicon oxide thin film becomes 500 °
Set to minutes. 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) Silicon monoxide (purity 99.5%, particle size 3-5 mm, manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used as an evaporation source, and oxygen gas was supplied at a flow rate of 150 sccm near the coating drum of the chamber. The pressure in the chamber at the time of film formation was set to 3 × 10 ⁻³ Torr, and the running speed of the base film was set to 120 m / min so that the thickness of the silicon oxide thin film was 500 °. In the same manner as in Sample 1, a transparent barrier film of the present invention (Sample 2) was obtained. The composition of the formed silicon oxide thin film was SiO _y (y = 1.8). Example 3 Using silicon (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity: 99.997%, particle size: 2 to 5 mm) as an evaporation source, oxygen gas was introduced into the chamber near the coating drum at a flow rate of 300 sccm. The pressure in the chamber at the time of film formation was set to 5 × 10 ⁻³ Torr, and the running speed of the base film was set to 80 m / min so that the thickness of the silicon oxide thin film was 500 °. In the same manner as in Sample 1, a transparent barrier film of the present invention (Sample 3) was obtained. The composition of the formed silicon oxide thin film was SiO _y (y = 1.8). (Example 4) A roll-shaped biaxially stretched polyethylene terephthalate film (Lumirror S-10 manufactured by Toray Industries, Inc., thickness 12 μm, width 600 mm, length 50) as a base film
00m) was prepared and mounted in a chamber of a take-up type ion plating apparatus. Next, the pressure in the chamber was reduced to an ultimate vacuum of 5 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump.

Further, as an evaporation source, silicon dioxide (manufactured by Merck Japan KK, purity: 99.7%, particle diameter: 1 to 5 mm) was prepared and placed in a copper crucible.

Next, argon gas was introduced at a flow rate of 100 sccm near the coating drum of the chamber, and the degree of opening and closing of a valve between the vacuum pump and the chamber was controlled to reduce the pressure in the chamber during film formation. 2x
It was kept at 10 ^-2 Torr. Then, the evaporation source in the copper crucible was heated to evaporate, and 13.5 mm was applied to the coating drum.
A thin film of silicon oxide (SiO _y (y = 1.8)) was formed on the base film while a high frequency voltage of 6 MHz was applied. The traveling speed of the base film was set at 150 m / min so that the thickness of the silicon oxide thin film was 500 °. Also,
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 4) of the present invention was obtained. (Example 5) Silicon monoxide (purity 99.5%, particle size 3 to 5 mm, manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used as an evaporation source, and oxygen gas was supplied at a flow rate of 250 sccm near the coating drum of the chamber. The pressure in the chamber at the time of film formation was set to 3 × 10 ⁻² Torr, and the running speed of the base film was set to 100 m / min so that the thickness of the silicon oxide thin film was 500 °. In the same manner as in Sample 4, a transparent barrier film of the present invention (Sample 5) was obtained. The composition of the formed silicon oxide thin film was SiO _y (y = 1.7). (Example 6) Using silicon (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity: 99.997%, particle size: 2 to 5 mm) as an evaporation source, introducing oxygen gas at a flow rate of 500 sccm near the coating drum of the chamber. The pressure in the chamber at the time of film formation was set to 5 × 10 ⁻² Torr, and the running speed of the base film was set to 80 m / min so that the thickness of the silicon oxide thin film was 500 °. In the same manner as in Sample 4, a transparent barrier film of the present invention (Sample 6) was obtained. The composition of the formed silicon oxide thin film was SiO _y (y = 1.7). (Comparative Example 1) A roll-shaped biaxially stretched polyethylene terephthalate film (Lumirror S-10 manufactured by Toray Industries, Inc., thickness 12 μm, width 600 mm, length 50) as a base film
00m) was prepared and mounted in a chamber of a roll-up type vacuum evaporation apparatus. Next, the inside of the chamber was reached at an ultimate vacuum of 5 × 10 by an oil rotary pump and an oil diffusion pump.
^The pressure was reduced to ^-5 Torr.

As an evaporation source, silicon monoxide (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity: 99.5%, particle size: 3 to 5 mm)
Was prepared and placed in a copper crucible.

Next, oxygen gas was introduced into the vicinity of the coating drum of the deposition chamber at a flow rate of 0.5 slm, and the degree of opening and closing of a valve between the vacuum pump and the deposition chamber was controlled. Internal pressure 3
× 10 ⁻³ Torr. Then, the evaporation source in the copper crucible is heated and evaporated, and silicon oxide (SiO _y (y = 1.2) is formed on the base film running on the coating drum.
4) A thin film was formed. The traveling speed of the base film is
150 m / m so that the thickness of the silicon oxide thin film becomes 500 °
Set to minutes. 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 (Comparative Sample 1) was obtained. (Comparative Example 2) Using silicon dioxide (manufactured by Merck Japan KK, purity: 99.7%, particle size: 1 to 5 mm) as an evaporation source, introducing oxygen gas at a flow rate of 300 sccm near the coating drum of the chamber, Comparative samples except that the pressure in the chamber during film formation was set to 2 × 10 ⁻³ Torr, and the running speed of the base film was set to 100 m / min so that the thickness of the silicon oxide thin film was 500 °. In the same manner as in Example 1, a transparent barrier film (Comparative Sample 2) was obtained. The composition of the formed silicon oxide thin film was SiO _y (y = 1.8). (Evaluation) The refractive index of the silicon oxide thin film of each transparent barrier film produced as described above was measured as follows, and the results are shown in Table 1 below.

Refractive index ellipsometry (UVI manufactured by Jobin Yvon)
SEL), and measured over the entire visible light range.
The measured value at 33 nm was defined as the refractive index.

For each of the transparent barrier films produced as described above, the oxygen permeability, the water vapor permeability, and the suitability for post-processing and filling / packaging were measured and evaluated under the following conditions. 1 is shown.

Oxygen permeability Oxygen gas permeability measuring device (OX manufactured by Modern Control Co., Ltd.)
TRAN 2/20), temperature 23 ° C, humidity 50%
Measured at RH.

Practical level of oxygen barrier property: 6.0 cc /
m ² · day · atm or less Water vapor permeability Water vapor permeability measurement device (PER manufactured by Modern Control Co., Ltd.)
MATRAN-W3 / 31) at a temperature of 38 ° C. and a humidity of 100% RH.

Practical level of water vapor barrier property: 6.0 g /
m ² · day · atm or less Post-processing suitability / fill-packing suitability Using an adhesive consisting of a 7% solution of a two-component curable polyurethane resin, an adhesive layer (thickness) was formed on the silicon oxide thin film of each transparent barrier film produced. 1 μm). Then
A low-density polyethylene was extrusion-coated on the primer layer to form a heat-sealable resin layer having a thickness of 60 μm, thereby producing a laminated material having a layer configuration as shown in FIG. 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 heated. Fused to produce a filled packaging product. Suitability in this series of processing was evaluated based on the following criteria, and the result was regarded as post-processing suitability and filling / packing suitability.

(Evaluation Criteria) は: There was no defect in appearance, and the contents were not deteriorated at all after several days in a normal environment, and freshness was maintained.

×: Defects appeared on the appearance, or the contents were remarkably deteriorated after several days in a general environment.

[0067]

[Table 1] As shown in Table 1, the transparent barrier films of the present invention (Samples 1 to 6) each had excellent barrier properties and post-processing suitability,
It was confirmed that it had suitability for filling and packaging and was also excellent in transparency.

On the other hand, Comparative Sample 1 had good barrier properties, suitability for post-processing and suitability for filling and packaging, but was colored and lacked transparency. Further, Comparative Sample 2 was significantly inferior in both oxygen barrier property and water vapor barrier property as compared with the transparent barrier film of the present invention, and was insufficient in post-processing suitability and filling / packaging suitability.

[0069]

As described in detail above, according to the present invention, a silicon oxide film (SiO _y ) formed by ion plating using SiO _x (0 ≦ x ≦ 2) as an evaporation source.
The barrier layer composed of (1.5 ≦ y ≦ 2) has excellent transparency, is dense and has high barrier properties and impact resistance. Therefore, the transparent barrier film provided with such a barrier layer is It is excellent in transparency, does not generate cracks due to bending and the like, can stably maintain a high barrier property, and has a high cost of silicon monoxide (Si) as an evaporation source.
Silicon oxide other than O) can be used, and further, there is no environmental problem at the time of disposal and no dependence on the barrier property against humidity.
The laminated material using this transparent barrier film has post-processing suitability with a heat-sealable resin layer in addition to the above-described properties. It has excellent suitability for filling and packaging of materials and 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 schematic diagram illustrating an example of a hollow cathode ion plating apparatus used for manufacturing 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.

[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 sealing resin layer 24,34 ... Base material 35 ... Heat-sealing resin layer 51,61 ... Packing container 101 ... Hollow cathode type ion plating apparatus 102 ... Vacuum chamber 104 ... Coating drum 107 ... Hollow cathode type plasma gun 115 ... Raw material

Continued on the front page F-term (reference) 3E064 AA01 BA22 BA26 BA29 BA30 BA35 BA36 BA37 BA54 BA55 BA60 BB03 BC08 BC13 BC20 FA01 3E086 AA23 AC07 AD01 BA04 BA15 BA40 BB01 BB22 BB51 CA01 4F100 AA21B AK01A AK01 BAK AK04 BAK AK04 BAK AK04 BAK BA05 BA06 BA07 BA10B BA10C DA01 EH66B EJ38A GB15 JD01B JK10 JL12C JN01 JN18B YY00B

Claims (10)

[Claims] Claims: 1. The method according to claim 1, further comprising: a base film, and a barrier layer provided on at least one surface of the base film, wherein the barrier layer includes SiO _x (0 ≦ x ≦
A transparent barrier film comprising a thin film mainly composed of silicon oxide (SiO _y (1.5 ≦ y ≦ 2)) formed by ion plating using 2). 2. The transparent barrier film according to claim 1, wherein the silicon oxide film has a refractive index at a wavelength of 633 nm in a range of 1.45 to 1.60. 3. The transparent barrier film according to claim 1, wherein the ion plating is a hollow cathode type ion plating. 4. The substrate film according to claim 1, wherein the base film is any one of a biaxially oriented polypropylene film, a biaxially oriented polyamide film, and a biaxially oriented polyethylene terephthalate film. A transparent barrier film as described in Crab. 5. A laminate comprising a heat-sealing resin layer provided on at least one surface of the transparent barrier film according to claim 1. 6. A laminated material, wherein a heat-sealing resin layer is provided on a barrier layer of the transparent barrier film according to any one of claims 1 to 4. 7. The method according to claim 6, wherein a substrate is laminated on a substrate film on which no barrier layer is formed.
The laminated material according to the above. 8. The laminated material according to claim 7, wherein a heat-sealing resin layer is provided on the base material. 9. The laminate according to claim 5, further comprising an anchor coat agent layer and / or an adhesive layer between the barrier layer and the heat-sealing resin layer. 10. A packaging container obtained by using the laminated material according to any one of claims 4 to 9 to form a bag or a box by heat-sealing a heat-sealable resin layer.