JP2000263686A - Translucent barrier film, laminated material using the same and packaging container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a translucent barrier film having high barrier properties and excellent in impact resistance, a laminated material having post-processing aptitude and a packaging container good in filling and packaging aptitude of content. SOLUTION: A barrier layer 3 comprising a thin film based on SiOx (wherein x is 0.01-1.2) is provided on at least one surface of a substrate film 2 to constitute a translucent barrier film 1 with average light transmissivity of 10-70% at a wavelength of 400-700 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Hitherto, various packaging materials having a barrier property against oxygen gas and water vapor and having good storage suitability for foods and pharmaceuticals have been developed and proposed. There has been proposed a transparent barrier film having a configuration in which a coating layer of polyvinylidene chloride or ethylene vinyl alcohol copolymer is provided on a conductive plastic substrate.

[0003] However, these transparent barrier films have insufficient barrier properties against oxygen and water vapor.
In particular, there is a problem that the barrier property is significantly reduced in the sterilization treatment at a high temperature. 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.

Therefore, in recent years, a transparent barrier film having a structure in which a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on a flexible plastic base material, a packaging laminate using the same, Packaging containers and the like have been proposed.

[0005] 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 a high barrier property against water vapor, oxygen gas and the like, a fragrance retention property, and the like. There is almost no impact on the environment, and the demand for packaging materials and others is greatly expected.

[0006]

On the other hand, in the case of some foods, pharmaceuticals, etc., in order to maintain quality due to the nature of the contents,
In some cases, the packaging material is required to have a high light-shielding property as well as a high barrier property against water vapor and oxygen gas. From the viewpoint of quality maintenance, an opaque packaging material that completely blocks light as a light-shielding property is preferable, but a translucent packaging material is sometimes desired from the viewpoint that contents can be confirmed. For example, in the pharmaceutical field, colored glass bottles are used. This colored glass bottle has a translucent light shielding property, and
Since it has high barrier properties against water vapor, oxygen gas, etc.
It is an ideal material from the viewpoint of maintaining the quality of the contents.

However, a packaging material made of a glass material has a problem that it is heavy, has poor impact resistance, and is accompanied by danger in some cases. In addition, from the viewpoint of reducing the weight of the packaging material and improving the impact resistance, the plastic material is excellent. However, it is necessary to provide a barrier property against oxygen and hydrogen in addition to providing a light-shielding property. Is currently not available.

[0008] The present invention has been made in view of such circumstances, and a translucent barrier film having high barrier properties and excellent impact resistance, and a laminated material having post-processing suitability. It is an object of the present invention to provide a packaging container having good filling and packaging suitability for contents.

[0009]

In order to achieve the above object, a translucent barrier film of the present invention comprises a base film and a barrier layer provided on at least one surface of the base film. At least, the barrier layer is Si
It is a thin film mainly composed of O _x (X is in the range of 0.01 to 1.2), and has a configuration in which the average light transmittance at a wavelength of 400 to 700 nm is in the range of 10 to 70%.

[0010] The translucent barrier film of the present invention comprises:
At least a base film and a barrier layer provided on at least one surface of the base film, wherein the barrier layer is a thin film mainly composed of AlO _x (X is in the range of 0.2 to 1.2). And the average light transmittance at a wavelength of 400 to 700 nm is in the range of 10 to 70%.

Further, the translucent barrier film of the present invention is configured such that the thickness of the barrier layer is in the range of 100 to 3000 °.

Further, the translucent 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.

Further, the translucent barrier film of the present invention has a configuration in which the barrier layer is formed by any one of a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD). .

The laminate of the present invention has a structure in which a heat-sealing resin layer is provided on at least one surface of the above-mentioned translucent 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 translucent barrier film, and a base material is provided on a base material film on which no barrier layer is formed. It was configured to be provided by lamination, and further to be configured to be provided with a heat-sealing resin layer on a 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 is translucent and has a light-shielding property, and at the same time, it is dense and imparts extremely high barrier properties and impact resistance to the translucent barrier film. The laminated material is provided with post-processing suitability by the heat-sealable resin layer in addition to the above-described properties, and the packaging container formed from the laminated material in a bag or box is provided with excellent contents filling and packaging suitability. .

[0019]

Next, an embodiment of the present invention will be described with reference to the drawings.

Translucent barrier film FIG. 1 is a schematic sectional view showing one embodiment of the translucent barrier film of the present invention. In FIG. 1, the translucent barrier film 1 includes 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 a barrier layer 3 on both sides of the base film 2.

(Base Film) The base film 2 constituting the translucent 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. It can be appropriately selected from the purpose and the like. 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,
Elongation (uniaxial or biaxial) of saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin, etc.
Alternatively, an unstretched flexible transparent resin film can be used. The thickness of the base film 2 is 5 to 500 μm.
m, preferably within the range of 10 to 100 μm.

Further, the base film 2 as described above may be one having its surface coated with an anchor coat agent or the like and, if necessary, subjected to a surface smoothing treatment or the like.

(Barrier Layer) The barrier layer 3 constituting the translucent barrier film 1 of the present invention is a thin film mainly composed of silicon oxide SiO _x (X is in the range of 0.01 to 1.2), or aluminum oxide. The barrier layer 3 is a thin film mainly composed of AlO _x (X is in the range of 0.2 to 1.2).
Wavelength of the translucent barrier film 1 provided with
The average light transmittance in nm is in the range of 10-70%. Although the thin film mainly composed of SiO _x or AlO _x has higher transparency as the oxygen amount increases, the present invention
By controlling the amount of oxygen, the total light transmittance is controlled,
The light-shielding property is realized while maintaining the light-transmitting property enough to confirm the contents.

When the barrier layer 3 is a thin film mainly composed of SiO _x , the oxygen amount X can be set in the range of 0.01 to 1.2. The lower limit 0.01 of the oxygen amount X was set in consideration of slight oxidation that occurs when a semi-transparent barrier film 1 is obtained by forming a barrier layer by a film formation method described later using pure silicon. Things. On the other hand, when the oxidation amount X exceeds 1.2, the transparency of the barrier layer is increased, and even if the barrier layer has a maximum thickness as described below without lowering the barrier property, the wavelength of the translucent barrier film 1 is 400 to 700 nm.
In this case, the average light transmittance exceeds 70%, and the light-shielding property is undesirably reduced.

When the barrier layer 3 is a thin film mainly composed of AlO _x , the oxygen amount X can be set in the range of 0.2 to 1.2. When the oxygen amount X is less than 0.2, sufficient barrier properties (oxygen permeability is 5 cc / m ² · day · at
m or less, and the water vapor transmission rate indicates about 5 g / m ² · day · atm or less), even if the minimum thickness as described below is required to secure the translucent barrier film 1 at a wavelength of 400 to 700 nm. Has an average light transmittance of 10
%, The appropriate transparency cannot be obtained. Further, when the oxidation amount X exceeds 1.2, the transparency of the barrier layer 3 increases, and even if the maximum thickness (which will be described later) can be set without lowering the barrier property, the translucent barrier film 1
Average light transmittance at a wavelength of 400 to 700 nm of 7
If it exceeds 0%, the light-shielding property becomes insufficient.

The barrier layer 3 has a thickness of 100 to 30.
The average light transmittance at a wavelength of 400 to 700 nm of the translucent barrier film 1 can be appropriately set in the range of 00 °, preferably 100 to 1000 °, in the range of 10 to 70%. The thickness of the barrier layer 3 is 100 mm
If it is less than 3, the barrier layer 3 cannot exhibit sufficient barrier properties (the oxygen permeability is about 5 cc / m ² · day · atm or less, and the water vapor permeability is about 5 g / m ² · day · atm or less), If it exceeds 3000 °, on the other hand, the barrier properties decrease, and the time required for film formation is undesirably increased.

The barrier layer 3 is made of SiO _x , which is mainly composed of SiO _x.
Alternatively, in addition to AlO _x , metals such as aluminum, magnesium, calcium, potassium, sodium, titanium, zirconium, and yttrium, and nonmetallic elements such as carbon, boron, nitrogen, and fluorine may be contained.

In the present invention, the above-mentioned barrier layer 3 may be subjected to a surface treatment such as a corona treatment, a plasma treatment, a silane coupling agent treatment or the like for the purpose of improving the post-processing suitability.

The formation of the barrier layer 3 on the base film 2 can be performed by a conventionally known thin film forming method.
For example, in the case of the barrier layer 3 mainly composed of SiO _x , it can be formed by any one of a vacuum evaporation method, a sputtering method, and a chemical vapor deposition method (CVD). In the case of the barrier layer 3 mainly composed of AlO _x , the barrier layer 3 can be formed by any one of a vacuum deposition method and a sputtering method.

Laminated Material Next, the laminated material of the present invention will be described with reference to an example using the above-mentioned translucent barrier film 1 of the present invention.

FIG. 2 is a schematic sectional view showing an embodiment of the laminated material of the present invention. In FIG. 2, a laminated material 11 includes a translucent 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 translucent barrier film 1. Agent layer 12
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,
It is formed by 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 a polybutadiene type. be able to. The adhesive layer 12 is formed by coating the above-described laminating adhesive by, for example, roll coating, gravure coating, knife coating, deb coating, spray coating, or other coating methods, 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. 3 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 3, a laminated material 21 includes a translucent barrier film 1 having a barrier layer 3 on one surface of a base film 2, and an anchor coating agent layer and / or an adhesive layer on the barrier layer 3 of the translucent barrier film 1. The translucent barrier film 1 includes a heat-sealable resin layer 23 formed through an agent layer 22 and a substrate 24 provided on the other surface (non-barrier layer forming surface) of the base film 2 of the translucent 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.

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 24 is a basic material, it has excellent properties in mechanical, physical, chemical, etc., and particularly has strength. A resin film or sheet that 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, for example, a character, a figure, a symbol, a picture, or a pattern is printed on the base material 24 by a normal printing method. Is also good. Such characters and the like can be visually recognized through the translucent barrier film 1 constituting the laminated material 21.

FIG. 4 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 4, a laminated material 31 includes a translucent 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 translucent barrier film 1. A heat-sealable resin layer 33 formed via the agent layer 32, a base material 34 provided on the other surface (non-barrier layer forming surface) of the base film 2 of the translucent barrier film 1,
4 and a heat-sealing resin layer 35 formed thereon.

The anchor coating agent layer, the adhesive layer 32 and the heat-sealable resin layers 33 and 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 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, a wet lamination method, a dry lamination method, a solventless dry lamination method, an 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 a bag made or box-formed 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, etc. By fusing to form a seal portion, various types of packaging containers according to the present invention can be manufactured.

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

FIG. 5 is a perspective view showing one embodiment of the packaging container of the present invention as described above. In FIG. 5, a packaging container 51 is obtained by laminating a set of laminated materials 11 of the present invention so that the heat-sealable resin layers 13 thereof 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 may be, for example, a self-standing packaging bag (standing pouch) or the like. Further, a tube container or the like may be manufactured 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.

In the packaging container of the present invention, first, a blank plate for producing a desired container is prepared using the laminated material of the present invention, and the trunk, bottom,
By forming the head and the like, for example, a brick type, flat type or Goebel top type liquid container or the like can be manufactured. Further, the shape can be manufactured in any shape such as a rectangular container and a cylindrical can such as a round shape.

FIG. 6 is a perspective view showing an embodiment of the above-mentioned liquid-filled paper container which is a packaging container of the present invention, and FIG. 7 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. 4, 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 can be used for 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. It is suitably used for filling and packaging of foods, pharmaceuticals and the like that require light-shielding properties for maintenance.

[0056]

Next, the present invention will be described in more detail with reference to examples.

Example 1 A sheet-shaped biaxially stretched polyethylene terephthalate film (Lumirror S-10 manufactured by Toray Industries, Ltd., thickness 25 μm, size 20) was used as a base film.
(0 mm x 150 mm) was prepared and placed in a chamber of a batch type vacuum evaporation apparatus (BMC-700 manufactured by SYNCHRON). Next, the inside of the chamber was reached at an ultimate vacuum of 5 × 10 ⁻⁶ Torr by an oil rotary pump and an oil diffusion pump.
The pressure was reduced to r. Further, silicon monoxide SiO is used as an evaporation source.
(Manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.5%, particle size 3
５5 mm) and placed in a copper crucible. The evaporation source was heated using an electron gun and a power of about 1 kW was applied.
Then, an oxygen gas was supplied into the chamber at a flow rate of 10 sccm, and a barrier layer was formed under an oxidizing atmosphere.
The film thickness of the barrier layer was monitored up to 3,000 ° by monitoring the film thickness during vapor deposition using a quartz crystal film thickness meter. The pressure in the chamber during this film formation was 1 × 10 ⁻⁴ Torr. Thereby, the translucent barrier film of the present invention was obtained.

The translucent barrier film thus produced has an average light transmittance of 65% at a wavelength of 400 to 700 nm and an oxygen transmittance of 4.5 cc / m ² · day · at.
m, the water vapor transmission rate was 4.0 g / m ² · day · atm, and the film had light-shielding properties, appropriate transparency, and excellent barrier properties. The oxygen content of silicon oxide SiO _x constituting the barrier layer was X = 1.2.

Further, a plastic bag of a three-side seal type as shown in FIG. 5 was manufactured using the above-mentioned translucent barrier film, and ham was filled as the content and left for 7 days. The suitability for post-processing of the transparent barrier film and the suitability for filling and packaging of the packaging container in this series of processing were good, and the quality of the contents after standing was good.

The average light transmittance, the oxygen transmittance, the water vapor transmittance, and the composition of the barrier layer at a wavelength of 400 to 700 nm were measured by the following methods. In addition, evaluation of suitability for post-processing, suitability for filling and packaging, and suitability for quality maintenance were performed by the following methods.

Average light transmittance and spectral transmittance measurement device at a wavelength of 400 to 700 nm (UV-31 manufactured by Shimadzu Corporation)
00), the spectral transmittance of 400 to 700 nm was measured, and the average transmittance was calculated by calculation.

Oxygen permeability Oxygen gas permeability measuring device (MOC manufactured by Modern Control Co., Ltd.)
ON OXTRAN) at a temperature of 23 ° C. and a humidity of 50% RH.

Water vapor transmission rate Water vapor transmission rate measuring apparatus (MOCON manufactured by Modern Control Co., Ltd.)
PERMATRAN), temperature 38 ° C, humidity 100% RH
Was measured.

The composition of the barrier layer was measured by X-ray photoelectron spectroscopy (XPS).

Suitability for post-processing, suitability for filling and packaging, suitability for quality maintenance Using an adhesive consisting of a 7% solution of a two-component curable polyurethane resin, an adhesive layer (thickness: 1 μm) was formed on the barrier layer of the translucent barrier film produced. Was formed. 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, thereby producing a laminated material having a layer configuration as shown in FIG. next,
Using this laminated material, a three-side sealed plastic bag as shown in FIG. 5 is manufactured by making a bag with a bag making machine, and the plastic bag is filled with ham whose discoloration of the contents can be easily judged by color. After that, the opening was heat-sealed to produce a filled packaged product, and the suitability in this series of processing was evaluated. The quality of the contents after the filled packaged product was left at 30 ° C. for 7 days was inspected.

(Comparative Example 1) The oxygen introduction flow rate during film formation was 20
A barrier film was produced in the same manner as in Example 1 except that the sccm was used. As a result of measuring the average light transmittance of this barrier film at a wavelength of 400 to 700 nm in the same manner as in Example 1, it was 80%, and the light-shielding properties were insufficient. Further, silicon oxide S constituting the barrier layer
The oxygen content of iO _x was X = 1.4.

(Comparative Example 2) The thickness of the barrier layer was set to 500
A barrier film was produced in the same manner as in Example 1 except that the symbol “Å” was used. As a result of measuring the average light transmittance of this barrier film at a wavelength of 400 to 700 nm in the same manner as in Example 1, it was 75%, and the light-shielding properties were insufficient.

Comparative Example 3 A barrier layer having a thickness of 600
A barrier film was produced in the same manner as in Example 1 except that the angle was set to 0 °. Example 1 of this barrier film
As a result of measuring the average light transmittance, the oxygen transmittance, and the water vapor transmittance at a wavelength of 400 to 700 nm in the same manner as in the above, the average light transmittance was 55%, and the light-shielding property and the appropriate transparency were provided. Has an oxygen permeability of 10.0c
c / m ² · day · atm, water vapor transmission rate 8.0 g /
m ² · day · atm, and the barrier properties were insufficient.

Example 2 A sheet-shaped biaxially stretched polyethylene terephthalate film (Lumirror S-10 manufactured by Toray Industries, Ltd., thickness 25 μm, size 20) was used as the base film.
(0 mm x 150 mm) was prepared and placed in a chamber of a batch type sputtering apparatus (SPF-530H manufactured by Anelva).

Next, the ultimate vacuum degree of 1 × 10 ⁻⁶ Torr was set in the chamber by an oil rotary pump and an oil diffusion pump.
The pressure was reduced to Further, as a target, single crystal silicon to which boron is added (manufactured by Mitsubishi Materials Corporation, purity 99.9)
999%, diameter 150 mm). Then, using a DC power source, a power of about 1 kW is applied to perform sputtering, and at the same time, an oxygen gas and an argon gas are introduced into the chamber at a flow rate of 1 sccm and 30 sccm, respectively. By controlling the degree of opening and closing of the valve, the pressure in the chamber during film formation can be increased to 4 × 10 ⁻³ To.
rr. By forming the film for one minute, a barrier layer having a thickness of 100 ° was formed. Thereby, the translucent barrier film of the present invention was obtained.

The translucent barrier film thus produced was evaluated in the same manner as in Example 1, and as a result, the wavelength
The average light transmittance at 700 nm is 15%, the oxygen transmittance is ^2.5 cc / m ² · day · atm, and the water vapor transmittance is 3.0 g / m ² · day · atm. It had good barrier properties. Further, the oxygen amount of SiO _x constituting the barrier layer was X = 0.1.

Further, a three-side sealed plastic bag was produced in the same manner as in Example 1 using the above-mentioned translucent barrier film, and ham was filled as the content and left for 7 days.
The suitability for post-processing of the transparent barrier film and the suitability for filling and packaging of the packaging container in this series of processing were good, and the quality of the contents after standing was good.

Comparative Example 4 A barrier film was produced in the same manner as in Example 2, except that the film formation time was 10 minutes and the thickness of the barrier layer was 1000 °. About this barrier film, wavelength 400-700 like Example 1.
As a result of measuring the average light transmittance in nm, it was 5%, and the film was not translucent.

Example 3 Metal aluminum (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%, particle size: 2 to 5 mm) was used as an evaporation source, and the oxygen gas introduction flow rate into the chamber was 5 sccm. Other than that, as in Example 1, while monitoring the film thickness during vapor deposition with a quartz crystal film thickness meter, 10
A barrier layer mainly composed of aluminum oxide was formed by forming a film up to 00 °. Thereby, the translucent barrier film of the present invention was obtained.

The translucent barrier film thus produced was evaluated in the same manner as in Example 1, and as a result, the wavelength
The average light transmittance at 700 nm is 40%, the oxygen transmittance is ^2.5 cc / m ² · day · atm, and the water vapor transmittance is 2.0 g / m ² · day · atm. It had good barrier properties. Further, the oxygen amount of AlO _x constituting the barrier layer was X = 0.9.

Further, a plastic bag of a three-sided seal type was produced in the same manner as in Example 1 using the above-mentioned translucent barrier film, and ham was filled as the content and left for 7 days.
The suitability for post-processing of the transparent barrier film and the suitability for filling and packaging of the packaging container in this series of processing were good, and the quality of the contents after standing was good.

Comparative Example 5 A barrier film was produced in the same manner as in Example 3 except that the flow rate of the introduced oxygen gas during film formation was set to 20 sccm. About this barrier film,
The average light transmittance at a wavelength of 400 to 700 nm was measured in the same manner as in Example 1. As a result, the average light transmittance was 85%, and the light-shielding properties were insufficient. Further, AlO constituting the barrier layer
The oxygen content of _x was X = 1.4.

Comparative Example 6 The thickness of the barrier layer was 400
A barrier film was produced in the same manner as in Example 3 except that the angle was set to 0 °. Example 1 of this barrier film
As a result of measuring the average light transmittance at a wavelength of 400 to 700 nm in the same manner as in the above, it was 7%, and it was a film having no light transmitting property.

[0079]

As described in detail above, according to the present invention, the battery
The rear layer is made of silicon oxide SiO_x(X is 0.01 to 1.2
Range) or aluminum oxide
AlO _x(X is in the range of 0.2 to 1.2)
A translucent barrier film comprising the barrier layer
Average light transmittance at a wavelength of 400 to 700 nm is 1
It is in the range of 0-70%, and it is moderately transparent with light shielding.
Excellent barrier properties and impact resistance with excellent flexibility
With no cracks due to bending
Barrier properties can be maintained stably and at the time of disposal
There are no environmental problems and no barrier dependence on humidity. This
The laminated material using the translucent barrier film of
Heat-sealing resin layer in addition to post-processing suitability
And made such a laminated material into a bag or box.
Packaging containers can maintain the quality of the contents and are suitable for filling and packaging.
Excellent in nature.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view showing one embodiment of a laminated material using the translucent barrier film of the present invention.

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

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

FIG. 5 is a schematic sectional view showing one embodiment of a packaging container using the translucent barrier film of the present invention.

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

FIG. 7 is a plan view of a blank plate used for manufacturing the packaging container shown in FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Translucent 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 sealable resin layer 51, 61 ... packaging container

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3E033 AA09 BA13 BA15 BA16 BA18 BA21 BB04 BB05 BB08 CA03 CA16 CA18 DB01 DD01 3E064 AA05 BA30 BA36 BA55 BC08 EA17 FA04 HE02 HF09 4F100 AA19B AA20B AK01A AK00A00AAT00A00AAR00A00AAR00AAR00A BA03 BA04 BA05 BA07 BA26 CB00 EH66B EJ38A GB16 GB23 JD02 JD02B JK10 JL01 JL12C JL12E JN01 JN01B JN08B YY00B

Claims (11)

[Claims] Claims: 1. A substrate film having at least a barrier layer provided on at least one surface of the substrate film, wherein the barrier layer is SiO _x (X is in the range of 0.01 to 1.2). And a wavelength of 400 to 700 n
A translucent barrier film, wherein the average light transmittance at m is in the range of 10 to 70%. 2. At least a substrate film and a barrier layer provided on at least one surface of the substrate film, wherein the barrier layer is made of AlO _x (X is in the range of 0.2 to 1.2). And a wavelength of 400 to 700 nm.
Wherein the average light transmittance is in the range of 10 to 70%. 3. The barrier layer has a thickness of 100 to 300.
The translucent barrier film according to claim 1 or 2, wherein the angle is within a range of 0 °. 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. The translucent barrier film described in Crab. 5. The method according to claim 1, wherein the barrier layer is formed by any one of a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD). The translucent barrier film according to any one of the above. 6. A laminate comprising a heat-sealing resin layer provided on at least one surface of the translucent barrier film according to claim 1. 7. A laminate comprising a heat-sealing resin layer provided on a barrier layer of the translucent barrier film according to claim 1. 8. The method according to claim 7, wherein a base material is laminated on a base film on which no barrier layer is formed.
The laminate according to item 1. 9. The laminated material according to claim 8, further comprising a heat-sealing resin layer on the base material. 10. The laminate according to claim 6, further comprising an anchor coat layer and / or an adhesive layer between the barrier layer and the heat-sealing resin layer. 11. A packaging container made by using the laminated material according to claim 6 and heat-sealing a heat-sealing resin layer to form a bag or a box.