JP2000025150A - Laminated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated material preventing the generation of a crack in a membrane of inorg. oxide having barrier function, having high barrier properties to oxygen gas or steam and useful for packaging, for example, food and drink, medicines, cosmetics, chemicals and other various articles, especially, confectionery, snack food or the like. SOLUTION: In a laminated material A obtained by laminating at least a base material film layer 1, a resin film layer 4 having a vapor deposition membrane of inorg. oxide and a heat sealable resin layer 5, a printing pattern layer 2 is provided to the base material film constituting the base material film layer 1 or the vapor deposition membrane of inorg. oxide of the resin film constituting the resin film layer 4 having the vapor deposition membrane of inorg. oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated material, and more particularly, to a laminate having excellent barrier properties against oxygen gas or water vapor, for example, various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, etc. In particular, the present invention relates to a laminate useful for filling and packaging confectionery, snack foods, and the like.

[0002]

2. Description of the Related Art Conventionally, as packaging materials for filling and packaging confectionery, snack foods and the like, packaging materials having various forms have been developed and proposed. Generally, a packaging material consisting of a five-layer specification consisting of a base film layer / printing layer / polyethylene resin layer / aluminum-deposited biaxially stretched polyethylene terephthalate film layer / polyethylene resin layer / unstretched polypropylene film layer is used for confectionery. It is used as a packaging material for filling and packaging snack foods and the like. Further, instead of the packaging material having the above-mentioned five-layer specification, for example, a packaging material having a two-layer specification of a base film layer / printing layer / laminate adhesive layer / aluminum-deposited unstretched polypropylene film layer is used. Materials or packaging materials having a three-layer specification of a base film layer / printing layer / polyethylene resin layer / aluminum-deposited unstretched polypropylene film layer have also been proposed.

[0003]

By the way, in packaging materials for filling and packaging confectionery, snack foods, etc., it is important that the contents of the confectionery, snack foods, etc. do not dislike deterioration or deterioration due to transmission of sunlight or the like. Of course, because we hate deterioration and deterioration due to the effects of oxygen gas and humidity,
It has a light-shielding property and oxygen gas of 1 cc /
It is strongly required that the high-barrier property of m ² · 24 hr · atm or less and water vapor be 1 g / m ² · day or less. However, such packaging materials do not always satisfy the high barrier properties as described above, and in particular,
Depending on the type of contents such as confectionery, snack foods, etc., furthermore, a high barrier property against oxygen gas or water vapor may be required.
The reality is that it is difficult to produce a sufficiently satisfactory packaged product with packaging materials having the above specifications. For example, in snack foods, in order to extend the quality assurance period, packaging products with nitrogen gas replacement may be manufactured, and in such cases, packaging materials having the above specifications are fully satisfactory. It is difficult to produce a packaging product that can be used. Furthermore, the above 2
A packaging material having specifications of up to three layers has the advantage of low cost, but not only has poor physical properties as a packaging material, but also has a barrier property against oxygen gas, water vapor, and the like. In particular, it is inferior in barrier properties to oxygen gas and has only oxygen gas barrier properties of about 10 to 20 cc / m ² · 24 hr · atm.
It is rarely used as a packaging material for filling and packaging snack foods and the like.

In recent years, as a barrier material against oxygen gas or water vapor, a plastic base material such as a polyester-based resin film or a polyamide-based resin film has been used instead of the above-described aluminum-deposited resin film or aluminum foil. An inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like is used on the surface of the substrate, and a physical vapor deposition method (PV) such as a vacuum deposition method, a sputtering method, or an ion plating method is used.
D method) or chemical vapor deposition (CV) such as plasma enhanced chemical vapor deposition, thermochemical vapor deposition, photochemical vapor deposition, etc.
A transparent barrier film formed by forming a thin film of the inorganic oxide by utilizing the method D) or the like has attracted attention. Thus,
The above-mentioned transparent barrier film is more suitable for incineration and disposal than an existing aluminum-deposited resin film, aluminum foil or a barrier material made of a polyvinylidene chloride-based resin coat film, and is suitable for environmental protection. As a material, there is an advantage that a transparent specification is possible from the viewpoint of the visibility of the contents, and the demand is greatly expected in the future. Usually, the transparent barrier film, on the surface of the inorganic oxide thin film, for example, to provide a desired printed picture layer or the like by printing or the like, or,
An adhesive for laminating or the like is coated to form an adhesive layer for laminating or the like, and then, on the surface of the printed picture layer or the surface of the adhesive layer, a substrate such as another resin film, paper base, or the like is formed. The laminated materials are laminated to produce laminated materials having various layer constitutions. The laminated materials are used, and the laminated materials are formed into bags or boxes to produce packaging containers having various forms. Thereafter, various contents are filled and packaged in the packaging container to produce packaged products of various forms.

[0005] In the above-mentioned transparent barrier film, the inorganic oxide thin film is an inorganic, vitreous film, and lacks flexibility, conformability, etc. and is extremely brittle. Things. For this reason, for example, as described above, a desired printed pattern layer or the like is directly provided on the surface of the inorganic oxide thin film by, for example, printing, or a laminating adhesive or the like is coated.
Post-processing, such as providing a laminating adhesive layer or the like, by, for example, directly contacting the printing impression cylinder or the like with the thin film surface of the inorganic oxide, or coating the adhesive When the roll or the like comes into direct contact, external conditions such as heat or pressure are directly applied to the surface of the inorganic oxide thin film, and are affected by the external conditions, such as cracks or the like. May occur. Thus, when cracks or the like occur in the inorganic oxide thin film, the function as a barrier film against oxygen gas, water vapor, etc. is lost, and the barrier property against oxygen gas, water vapor, etc. is significantly deteriorated. There is a problem that does not do. Furthermore, even when packaging products of various forms are manufactured as described above, if cracks or the like occur in the inorganic oxide thin film as described above, from the contents side, or from the outside, through the portion. Various components infiltrate, for example, peeling phenomena occur between layers of the laminated material constituting the packaging container, the laminate strength is significantly reduced, and in some cases,
There is also a problem that phenomena such as bag breakage occur and it is difficult to produce a sufficiently satisfactory packaged product. For this reason,
In the above transparent barrier film, in order to protect the inorganic oxide thin film, for example, via a heat buffer layer,
Lamination of a heat-sealing resin layer has also been proposed, but this is not a satisfactory condition. Therefore, the present invention prevents the occurrence of cracks and the like for a thin film of an inorganic oxide having a barrier function, and has a high barrier property against oxygen gas or water vapor, for example, food and drink, pharmaceuticals, cosmetics, chemicals, etc. It is an object of the present invention to provide a laminate useful for filling and packaging of various articles such as confectionery, snack foods and the like.

[0006]

As a result of various studies to solve the above problems, the present inventor has added external conditions such as heat or pressure to a thin film of inorganic oxide having a barrier performance. Focusing on laminating other substrates without performing, first, at least a substrate film layer, a resin film layer having a deposited film of inorganic oxide, and a heat-sealing resin layer In the laminate material, the printed pattern layer, in advance, a base film constituting the base film layer, or a non-inorganic oxide deposited film of a resin film constituting a resin film layer having an inorganic oxide deposited film On the side,
Next, a base film layer, a resin film layer having an inorganic oxide vapor-deposited film, and a heat-sealing resin layer, for example, between the respective layers, through an extruded resin layer by extrusion laminating, Laminate to produce laminated material, then
Using the laminated material, it is made into a bag or a box to produce packaging containers of various forms, and thereafter, various contents are filled and packaged in the packaging container to form various containers. No cracks were observed in the inorganic oxide thin film having the barrier function, and no peeling phenomenon was observed in the laminated material constituting the packaging container. -Excellent strength and high barrier property against oxygen gas or water vapor etc., for example, filling and packaging of various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, etc., especially confectionery, snack foods, etc. The present invention has been completed by finding that a laminated material useful for the present invention can be provided.

[0007] That is, the present invention provides a printed material layer comprising at least a base film layer, a resin film layer having an inorganic oxide deposited film, and a heat-sealing resin layer. A laminated film characterized by being provided on a substrate film constituting a substrate film layer, or a non-inorganic oxide deposited film side of a resin film constituting a resin film layer having an inorganic oxide deposited film. It is about.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to the drawings. First, the structure of the laminated material according to the present invention will be described with reference to the drawings by exemplifying 12 examples. FIGS. 1 and 2 show the layer structure of the laminated material according to the present invention. It is a schematic sectional drawing which shows.

First, as the laminated material A according to the present invention,
As shown in FIG. 1, at least a base film layer 1, a print pattern layer 2 provided on a base film constituting the base film layer 1, a resin film layer 4 having an inorganic oxide vapor-deposited film 3, and The heat-sealable resin layer 5 is extruded between the respective layers, and extruded resin layers 6, 6 by laminating.
And a configuration in which the layers are stacked via a. Or,
As the laminated material B according to the present invention, as shown in FIG.
At least a substrate film layer 1 and an inorganic oxide deposited film 3
A resin film layer 4 having: a printed pattern layer 2 provided on a non-inorganic oxide deposited film side p of the resin film constituting the resin film layer 4 having the inorganic oxide deposited film 3;
The heat-sealable resin layer 5 is formed by laminating the respective layers via the extruded resin layers 6, 6 by extruding the respective layers. The above examples illustrate the layer structure of the laminated material according to the present invention, and the present invention is not limited thereto. For example, in the laminated material according to the present invention, as shown in FIGS. 1 and 2 described above, the heat-deposited inorganic oxide-deposited film constituting the resin film layer having the inorganic oxide-deposited film is formed. Instead of being laminated so as to face the hydrophilic resin layer, it can also be laminated facing the base film layer. Further, in the laminated material according to the present invention, a base film layer, a resin film layer having an inorganic oxide vapor-deposited film, and an extruded resin layer formed by extruding each layer of a heat-sealing resin layer with a laminate. Instead of laminating through
A laminating adhesive or the like may be used, coated and laminated via a laminating adhesive layer by a dry laminating method.

Next, in the present invention, a method of manufacturing a laminated material according to the present invention will be described with reference to an example. Examples of such a manufacturing method include, although not shown, a base material forming a base film layer. On the back side of the material film, using a normal printing method, for example, characters, figures, patterns, symbols,
A desired printed pattern layer such as others is provided by printing, and on the other hand, on one surface of a resin film constituting a resin film layer having a vapor-deposited film of an inorganic oxide, for example, physical vapor growth, or chemical vapor growth Using a method or the like, providing a vapor-deposited film of an inorganic oxide, and then facing the printed pattern layer surface of the base film layer and the resin film layer surface of the resin film layer having the vapor-deposited inorganic oxide film, A heat-sealing resin layer is opposed to the surface of the inorganic oxide vapor-deposited film of the resin film layer having the above-mentioned inorganic oxide vapor-deposited film, and then, an extruded laminating resin is used between those layers. While extruding this, the extruded resin layer is extruded through the extruded resin layer.
Then, the laminated material according to the present invention can be manufactured. In the above, instead of providing a print pattern layer on the back surface of the base film constituting the base film layer, a print pattern layer is formed on the non-deposited film surface side of the resin film constituting the resin film layer having the inorganic oxide deposited film. Can also be provided.
The above exemplification is an example of the method for producing a laminate according to the present invention, and the present invention is not limited thereto.

Next, in the present invention, the materials, materials, and methods for producing the same used in the laminate according to the present invention will be described. First, the base material for forming the base film layer constituting the laminate according to the present invention is described. As a material film, for example, when constituting a packaging container, since it is a basic material, it has excellent properties in mechanical, physical, chemical, other, etc., especially, it has strength and toughness. And a heat-resistant resin film or sheet can be used. Specifically, for example, polyester-based resins, polyamide-based resins, polyaramid-based resins, polyolefin-based resins, polycarbonate-based resins Use strong resin films or sheets such as resin, polystyrene resin, polyacetal resin, cellulose resin, fluorine resin, etc. Can. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm.

Next, in the present invention, a resin film layer having an inorganic oxide vapor-deposited film constituting the laminate according to the present invention will be described. First, as the resin film constituting the resin film layer, an inorganic oxide is used. Various colorless and transparent resin films or sheets having a function of supporting the deposited film can be used.Specifically, for example,
Polyolefin resins such as polyethylene or polypropylene; polyester resins such as polyethylene terephthalate or polyethylene naphthalate; polyamide resins; polycarbonate resins; polystyrene resins; polyvinyl alcohol resins; -Saponified vinyl acetate copolymer, polyacrylonitrile resin,
Films or sheets of various resins such as acetal resins and others can be used. As the above resin film or sheet, a single layer, a film formed by a co-extrusion method of two or more layers, or a film stretched in a uniaxial or biaxial direction may be used. Can be formed, and the thickness thereof is about 5 to 100 μm, preferably 9 to 50 μm, from the viewpoint of stability during the production.
Position is desirable. In the present invention, depending on the application,
For example, desired additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, and the like are arbitrarily added within a range that does not affect the transparency, and a film or resin of the resin containing them is added.ト can also be used.

Next, in the present invention, the vapor-deposited inorganic oxide film constituting the resin film layer having the vapor-deposited inorganic oxide film will be described. Amorphous (amorphous)
Any type of thin film can be used,
For example, for example, silicon (Si), aluminum (A
l), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( A thin film in which an oxide of a metal such as Y) is made amorphous can be used. Thus, as a material suitable for a packaging material or the like, a thin film in which an oxide of a metal such as silicon (Si) or aluminum (Al) is made amorphous can be given. Thus, a thin film in which the above metal oxide is made amorphous can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. For example, SiO _x , AlO
_X , MgO _X, etc., where MO _X (where M is
It represents a metal element, and the value of X varies depending on the metal element. ). Further, as the range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, and magnesium (Mg) is
0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, and boron ( B) is 0 to
1, 5, 0 for titanium (Ti), 0 for lead (Pb)
-1, zirconium (Zr) can take a value of 0-2, and yttrium (Y) can take a value of 0-1.5.
In the above, when X = 0, it is a perfect metal, it is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention,
As a packaging material, generally, there are few examples of use except for silicon (Si) and aluminum (Al). Silicon (Si) is 1.0 to 2.0, aluminum (Al)
Can be used in the range of 0.5 to 1.5. In the present invention, the thickness of the thin film of the inorganic oxide as described above varies depending on the type of the metal or the metal oxide to be used.
It is desirable to arbitrarily select and form it within the range of 100 to 1000 °. Further, in the present invention, the inorganic oxide deposited film is not limited to one layer of the inorganic oxide thin film, but may be in the form of a laminate in which two or more layers are stacked. As the metal oxide, one type or a mixture of two or more types may be used to form a vapor deposited film of an inorganic oxide mixed with different materials.

Next, a method of forming a deposited film of an inorganic oxide in the present invention will be described. Examples of the method include a physical vapor deposition method (such as a vacuum deposition method, a sputtering method, and an ion plating method). Physica
l Vapor Deposition method, PVD
Method) or a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
medical Vapor Deposition method, CV
D method) and the like. More specifically, the above-mentioned metal oxide is used as a raw material, and a vacuum evaporation method of heating and vapor-depositing the metal oxide on a plastic substrate, or using a metal or metal oxide as a raw material, The deposited film can be formed by an oxidation reaction deposition method of introducing and oxidizing and depositing on a plastic substrate, and a plasma-assisted oxidation reaction deposition method of promoting the oxidation reaction by plasma. Further, in the present invention, when forming a deposited film of silicon oxide, the deposited film can be formed by a plasma chemical vapor deposition method using an organic silicon compound such as an organosiloxane as a raw material.

In the present invention, a specific example of the method for forming the above-described inorganic oxide vapor-deposited film is shown in FIG.
FIG. 1 is a schematic configuration diagram showing a configuration of an example of a winding type vacuum evaporation apparatus. In the present invention, as shown in FIG. 3, first, a resin film 14 constituting a resin film layer is unwound from an unwinding roll 13 in a vacuum chamber 12 of a winding type vacuum evaporation apparatus 11, and further, ,
The resin film 14 is guided to a cooled coating drum 17 via guide rollers 15 and 16. Next, in the present invention, after the resin film 14 is guided on the cooled coating drum 17 as described above, the surface of the resin film 14 is provided with a vapor deposition source 18 such as aluminum (metal) or aluminum oxide. Are put into the crucible 19, and the aluminum (metal) or aluminum oxide heated in the crucible 19 is evaporated. At this time, oxygen gas or the like is ejected from the oxygen outlet 20. , An aluminum oxide vapor-deposited film is formed through the masks 21 and 21, and then the resin film 14 on which the aluminum oxide vapor-deposited film is formed
Is wound up on a take-up roll 22 via guide rolls 16 'and 15', whereby a resin film layer having an inorganic oxide vapor-deposited film according to the present invention can be produced. In the present invention, the thickness of the thin film mainly composed of the deposited film of aluminum oxide as the deposited film of the inorganic oxide is preferably about 50 to 300 °, more preferably about 100 to 250 °. In the above description, if the thickness is more than 300 ° or even 250 °, the flexibility of the film is reduced and cracks or the like are easily generated in the film, which is not preferable. Also, the thickness is less than 50 ° or less than 100 °. It is not preferable because it is difficult to exhibit the effect such as the barrier property. In the above, for example, an electron beam (EB) method, a high-frequency induction heating method, a resistance heating method, or the like is used as a method for heating the deposition material. The above example is an example of the manufacturing method, and the present invention is not limited by this example.

Next, in the present invention, another example of a method for forming the above-mentioned inorganic oxide vapor-deposited film using a plasma enhanced chemical vapor deposition method will be described. FIG. 4 shows an example of a plasma chemical vapor deposition apparatus. FIG. 3 is a schematic configuration diagram illustrating FIG.
As shown in (1), first, a resin film 34 constituting a resin film layer is unwound from an unwinding roll 33 disposed in a vacuum chamber 32 of a plasma chemical vapor deposition apparatus 31, and further through an auxiliary roll 35. The cooling / electrode drum 36 is supplied at a constant speed. Then
In the present invention, the raw material volatile supply devices 37, 38, 39
Thus, for example, a vapor deposition mixed gas composed of a vapor deposition monomer gas such as an organic silicon compound, an oxygen gas, an inert gas, or the like is passed through the raw material supply nozzle 40 to the vapor deposition chamber-3.
2 and a glow discharge plasma 41 deposits an evaporated film of an inorganic oxide such as silicon oxide on the resin film 34 on the peripheral surface of the cooling / electrode drum 36 to form a film. . Thus, a predetermined voltage is applied to the cooling / electrode drum 36 from the power source 42 disposed outside the vacuum chamber 32, and a magnet 43 is disposed near the cooling / electrode drum 36. Then, the generation of the plasma 41 is promoted, and then the resin film 34 on which the deposited film of the inorganic oxide such as silicon oxide is formed is wound on the winding roll 45 via the auxiliary roll 44. Thus, a resin film layer having an inorganic oxide vapor-deposited film according to the present invention can be manufactured. In the drawing, reference numeral 46 denotes a vacuum pump.
The above example is an example of the manufacturing method, and the present invention is not limited by this example.

In the present invention, for example, the thin film layer of silicon oxide formed by the above-mentioned plasma chemical film forming method has the formula SiO _x (where X represents a number of 1 to 2). And a continuous thin film layer mainly composed of silicon oxide represented by the formula: SiO _x (where X represents a number of 1.3 to 1.9) from the viewpoint of transparency and the like. It is preferably a continuous thin film layer mainly composed of silicon oxide represented. The silicon oxide thin film layer is made of a silicon oxide compound containing silicon and oxygen as constituent elements, and is further made of one or more kinds of trace constituent elements made of carbon, hydrogen, silicon, or oxygen. It is composed of a continuous thin film layer of silicon oxide containing at least one compound. Further, the silicon oxide thin film layer is made of a silicon oxide compound containing silicon and oxygen as constituent elements,
Carbon, hydrogen, silicon, or at least one compound containing at least one element of oxygen, and the compound is formed from the film surface in a depth direction.
It consists of a continuous thin film layer of silicon oxide whose content has been reduced. Furthermore, the silicon oxide thin film layer
When a compound comprising carbon is contained, the carbon content is reduced in the depth direction of the film thickness. Thus, the film structure of the silicon oxide thin film layer described above may be, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Spectr) for the silicon oxide thin film layer formed by the above-described plasma chemical film formation method.
oscopy, XPS), secondary ion mass spectrometer (S
secondary Ion Mass Spectro
This can be confirmed by performing elemental analysis of the silicon oxide thin film layer surface using a method of performing analysis by ion etching in the depth direction or the like using a surface analysis device such as SCOPE (SIMS, SIMS) or the like. . In the present invention, the thickness of the thin film layer of an inorganic oxide such as silicon oxide,
A film having a thickness in the range of about 50 to 2000 ° can be formed. However, in the present invention, it is desirable that the thin film layer of an inorganic oxide such as silicon oxide is a thin film and has a film quality rich in flexibility and the like. It is desirable that the angle is about 300 °, more preferably about 100 ° to 250 °. In the above, when the film thickness exceeds 250 °, 300 °, and 2000 ° or the like, the flexibility and the like of the thin film layer tend to be inferior, and it is not preferable because cracks and the like tend to occur easily. The film thickness is 50mm,
Further, when the angle is less than 100 °, the oxygen gas barrier property, the water vapor barrier property and the like tend to be inferior. In the present invention, on one side of the substrate film layer as described above, a thin film layer of an inorganic oxide is formed by a plasma chemical film formation method, and on the surface of the thin film layer in the formed state,
For example, they are laminated without applying an external force such as heating, pressure, or the like.Thus, by laminating as described above, the occurrence of cracks or the like on the inorganic oxide thin film layer surface is suppressed. is there.

In the present invention, an organic silicon compound is used as a raw material for the silicon oxide vapor deposition film as described above.
A vapor-deposited film formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like can be used.
In the above description, examples of the organic silicon compound include:
1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, Vinyl trimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the above organosilicon compounds,
1.1.3.3-tetramethyldisiloxane or
The use of hexamethyldisiloxane as a raw material, due to its handleability, the characteristics of the formed deposited film, etc.
In particular, it is a preferred raw material. In the above, as the low-temperature plasma generator, for example, high-frequency plasma,
It is possible to use a generator such as a pulsed plasma or a microwave plasma. In the present invention, in order to obtain a highly active and stable plasma, it is necessary to use a generator based on a high-frequency plasma method. desirable.

Next, in the present invention, the heat-sealing resin layer constituting the laminated material according to the present invention is a resin film or sheet which can be melted by heat and adhered to each other.
And low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, and ionomer. Resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate 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,
Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. The resin film or sheet can be used. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film or film or sheet is 5μ.
m to 300 μm, more preferably 10 μm
About 100 μm is desirable.

In the present invention, the print pattern layer constituting the laminate according to the present invention may be, for example, a usual gravure ink composition, offset ink composition, relief ink composition, screen ink composition, or the like. Using ink compositions such as gravure printing, offset printing, letterpress printing, silk screen printing, etc., for example, characters, graphics, pictures, symbols, etc. It can be constituted by forming a desired print pattern layer composed of the above. In the above, various ink compositions include, for example, vehicles constituting the ink composition include, for example, polyethylene resins, polyolefin resins such as chlorinated polypropylene resins, poly (meth) acrylic resins, and polyvinyl chloride. Resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, Polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin, urea Resin, polyurethane resin, phenol resin, xylene resin, Cellulose resins such as ionic acid resin, nitrocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, petroleum resins, rosin, casein A mixture of one or more natural resins such as linseed oil, oils and fats such as linseed oil and soybean oil, and other resins can be used. Thus, in the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of colorants such as dyes and pigments are added thereto. , For example, fillers, stabilizers, plasticizers, antioxidants,
Light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents,
It is possible to use ink compositions in various forms obtained by arbitrarily adding additives such as a lubricant, an antistatic agent, a cross-linking agent, and the like and kneading them sufficiently with a solvent, a diluent or the like.

In the present invention, the resin forming the extruded resin layer by the extruded laminate constituting the laminated material according to the present invention may be, for example, low-density polyethylene, medium-density polyethylene, or high-density polyethylene. Polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer Copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methyl pentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid,
Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. Resin can be used. Thus, in the present invention, one or more of the above resins are used,
An extruded resin layer can be formed by John coating (extrusion coating). The film thickness is preferably about 5 μm to 100 μm, and more preferably about 10 μm to 70 μm.

Next, in the present invention, as the laminating adhesive constituting the laminating adhesive layer constituting the laminated material according to the present invention, specifically, for example, alkyl titanate or the like is used. Water-based or oil-based various organic titanium-based anchor coating agents, isocyanate-based anchor coating agents, polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, etc. Can be used. Thus, in the present invention, the above-mentioned anchor coating agent is, for example, roll-coated.
Coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods, and drying the solvent, diluent, etc. to constitute the laminated material of the present invention. An adhesive layer for lamination can be formed. In the above, the coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

In the present invention, examples of the laminating adhesive constituting the laminating adhesive layer constituting the laminated material according to the present invention include polyurethane-based, polyester-based, polyamide-based and epoxy-based adhesives. , Poly (meta)
Acrylic, polyvinyl acetate, polyolefin or modified polyolefin, casein, wax, ethylene- (meth) acrylic acid copolymer, polybutadiene,
Various types of laminating adhesives, such as a solvent type, an aqueous type, a non-solvent type, or a hot-melt type, in which others are the main components of the vehicle, can be used. Thus, in the present invention, as described above, the adhesive for laminating is, for example, roll coat, gravure coat, knife coat, dip coat, spray coat, and other coats. -Coating by the method
Then, the solvent, the diluent and the like are dried to form a laminating adhesive layer using the laminating adhesive according to the present invention. In the above, the application amount of the laminating adhesive is 0.1 to 5 g / m ² (dry state).
Position is desirable.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the laminated material constituting the packaging container. Required, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing, quality maintenance, workability,
Various conditions such as hygiene, etc. are required. For this reason, in the present invention, a material satisfying the above-described various conditions is arbitrarily selected and used, and these are laminated according to the above-described present invention. In addition to the material constituting the material, any desired additional material can be laminated to form a desired laminated material. Thus, in the above, specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer -Resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, 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-based) Resin), polyester resin, poly Mid resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluororesin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose And any other known resin film or sheet. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet can be used in any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 300 μm.
It can be used by selecting from a range of positions. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Particularly, in the laminated material according to the present invention, in order to protect the contents such as confectionery and snack food from permeation of sunlight and the like, for example, when light shielding property is required,
A black resin film, a white resin film, or a resin film colored in a desired color, and further formed by coating or printing one or more of the above ink compositions and the like. A laminated material can also be manufactured by laminating a colored layer or the like between layers constituting the laminated material.

Next, a method of manufacturing the laminated material according to the present invention using the above-mentioned materials in the present invention will be described. For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method,
T-die extrusion molding method, co-extrusion lamination method,
Inflation method, co-extrusion inflation method,
It can be performed by using other or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film, and for example, an isocyanate-based (urethane) System), polyethyleneimine system, polybutadiene system,
Known coating agents such as organic titanium-based anchor coating agents or polyurethane-based, polyacryl-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, and other laminating adhesives. Processing, anchor coating agents, adhesives and the like can be used.

Next, in the present invention, a method for producing a packaging container by making a bag or making a box using the above-described laminated material will be described. For example, the laminated material produced by the above-mentioned method is described. And heat-sealing the inner heat-sealable resin layer so that the heat-sealable resin layer faces the inner surface of the heat-sealable resin layer. A packaging bag can be manufactured by providing a package portion. Thus, as the bag making method,
The inner layer is bent with its surfaces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is formed, for example, into a side seal type, a two-way seal type, a three-way seal type, a four-way seal type. Seal type, seal type with envelope, seal type with seal (pillow seal type), seal type with folds, flat bottom type, square bottom type, etc. The heat seal depends on the heat seal form.
To produce various types of packaging containers according to the present invention. In addition, for example, a self-supporting packaging bag (standing pouch) can be manufactured,
Further, in the present invention, a tube container or the like can be manufactured by using the above laminated material. In the above, as a method of the heat seal, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like is used. Can be performed in the following manner. In the present invention, a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the present invention, when the packaging container contains a paper base, for example, as a laminated material,
Manufacture a laminated material obtained by laminating paper base materials, manufacture a blank plate from which a desired paper container is manufactured, and then make a body, a bottom portion, and a head using the blank plate, for example, ,
Brick type, flat type or gable-top type liquid paper containers 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.

In the present invention, the packaging containers produced as described above include, for example, various foods and beverages, chemicals such as adhesives and pressure-sensitive adhesives, various articles such as cosmetics, pharmaceuticals, and the like, especially confectionery. It is used for filling and packaging of snack foods and the like. Thus, the packaging container according to the present invention comprises:
As a barrier material, a resin film layer having an inorganic oxide vapor-deposited film is used. Thus, in the present invention, after the inorganic oxide vapor-deposited film is formed, the film is heated, pressured, etc. Without applying any external force, the base film or the like is laminated on the surface of the deposited inorganic oxide film in the state after film formation via an extruded resin layer by laminating, so that each layer is formed. Utilizing the effects of adhesiveness, flexibility, bending resistance, heat resistance, etc., the laminating strength between the layers can be remarkably increased, whereby the occurrence of cracks and the like in the inorganic oxide deposited film is minimized. As a result, it has strength and is excellent in various robustness, and is further excellent in barrier properties against oxygen gas, water vapor, etc., and is excellent in preservability of contents during storage / storage or distribution. The laminated material can be manufactured. Furthermore, in the present invention, after the packaging container or the like is used, when the packaging container is discarded as garbage and burned, there is no generation of harmful chlorine gas and the like, which is an advantage that it is extremely suitable for environmental protection. It has.

[0030]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 (1). Use a roll-up type vacuum evaporator,
A biaxially stretched polyethylene terephthalate film of μm as a base material, one side of which is subjected to an electron beam (EB) heating method using aluminum as an evaporation source, and a reactive vacuum evaporation method while supplying oxygen gas. Then, a deposited film of aluminum oxide having a thickness of 200 ° was formed. (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm was used, and a gravure ink composition was used on one surface thereof to form a desired print pattern layer using a gravure printing method. (3). Next, the thickness of the printed pattern layer of 20 μm was formed.
m, and a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm on which the above-mentioned vapor-deposited film of aluminum oxide is formed, using the former printed pattern layer surface and the latter biaxially oriented polyethylene terephthalate film. A low-density polyethylene was used between the layers with the turret film facing the surface, and while extruding it to a thickness of 15 μm, both were extruded and laminated. (4). Next, on the aluminum oxide deposited film surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the deposited aluminum oxide deposited film was formed,
In the same manner as described above, a low-density polyethylene is used, and while extruding it to a thickness of 15 μm, a non-stretched polypropylene film having a thickness of 20 μm, which is a sealant film, is extruded and laminated to obtain a laminate according to the present invention. Manufactured.

Embodiment 2 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and this film was mounted on a delivery roll of a plasma chemical film forming apparatus, and a silicon oxide thin film having a thickness of 180 ° was formed under the following film forming conditions. A layer was formed on one side of the biaxially oriented polyethylene terephthalate film described above. (Plasma chemical film formation conditions) Film formation speed; 100 m / min Plasma power; 10 kW Reaction gas mixture ratio; hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm, stander)
Doritter Minute, standard lit
er minute, the same applies hereinafter) Degree of vacuum in a vacuum chamber; 50 μbar (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm was used, and a gravure ink composition was used on one surface thereof to form a desired print pattern layer using a gravure printing method. (3). Next, the thickness of the printed pattern layer of 20 μm was formed.
m, and a biaxially oriented polyethylene terephthalate film having a thickness of 12 .mu.m on which a silicon oxide thin film layer is formed, using the former printed pattern layer surface and the latter biaxially oriented polyethylene terephthalate film. While facing the turret film surface, low density polyethylene is used between the layers, while extruding this to a thickness of 15 μm,
Both were extruded, laminated and laminated. (4). Next, a 12 μm-thick biaxially stretched polyethylene terephthalate having a silicon oxide thin film layer formed as described above was formed.
In the same manner as described above, a low-density polyethylene is used on the silicon oxide thin film layer surface of the film, and while extruding it to a thickness of 15 μm, an unstretched polypropylene film having a thickness of 20 μm as a sealant film is extruded and laminated. Thus, a laminated material according to the present invention was manufactured.

Embodiment 3 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. First, a desired printing pattern layer was formed on one surface of the film using a gravure ink composition using a gravure printing method. Next, using a winding type vacuum evaporation apparatus, the printed pattern layer was formed to a thickness of 12 μm.
m, a biaxially stretched polyethylene terephthalate film as a base material, and an electron beam (E) using aluminum as a vapor deposition source on the other side on which the printed picture layer is not formed.
B) A 200-nm-thick aluminum oxide vapor-deposited film was formed by a reactive vacuum vapor deposition method while supplying oxygen gas by a heating method. (2). On the other hand, a biaxially oriented polypropylene film having a thickness of 20 μm was prepared. (3). Next, the biaxially stretched polypropylene film and a printed pattern layer formed on one surface and a deposited film of aluminum oxide formed on the other surface having a thickness of 12 μm.
A biaxially-stretched polyethylene terephthalate film is used, one surface of the former is opposed to the surface of the deposited film of aluminum oxide, and a low-density polyethylene is used between the layers. While being extruded, both were extruded and laminated. (4). Next, a low-density polyethylene was used on the printed pattern layer surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the laminated printed pattern layer and the aluminum oxide film were formed as described above. Was extruded to a thickness of 15 μm, and a non-stretched polypropylene film having a thickness of 20 μm, which was a sealant film, was extruded and laminated to produce a laminate according to the present invention.

Embodiment 4 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. First, a desired printing pattern layer was formed on one surface of the film using a gravure ink composition using a gravure printing method. Next, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which a printed pattern layer was formed as described above was used, and was mounted on a delivery roll of a plasma chemical film forming apparatus. 18
A 0 ° silicon oxide thin film layer was formed on the other side of the biaxially stretched polyethylene terephthalate film on which the printed picture layer was not formed. (Plasma chemical film formation conditions) Film formation speed; 100 m / min Plasma power; 10 kW Reaction gas mixture ratio; hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm) Vacuum chamber Degree of vacuum in; 50 μbar (2). On the other hand, a biaxially oriented polypropylene film having a thickness of 20 μm was prepared. (3). Next, a biaxially stretched polypropylene film having a thickness of 20 μm and a printed pattern layer formed on one surface and a silicon oxide thin film layer formed on the other surface were formed to a thickness of 1 μm.
Using a 2 μm biaxially stretched polyethylene terephthalate film, one surface of the former is opposed to the surface of the silicon oxide thin film layer, and a low-density polyethylene is used between the layers and extruded to a thickness of 15 μm. Then, both were extruded and laminated. (4). Next, low-density polyethylene was used on the printed pattern layer surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the printed pattern layer and the silicon oxide thin film layer were formed as described above. Is 15μm thick
While extruding the sealant film to a thickness of 20
A laminated material according to the present invention was manufactured by extruding and laminating an unstretched polypropylene film having a thickness of μm.

Embodiment 5 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. First, a desired printing pattern layer was formed on one surface of the film using a gravure ink composition using a gravure printing method. Next, using a winding type vacuum evaporation apparatus, the printed pattern layer was formed to a thickness of 12 μm.
m, a biaxially stretched polyethylene terephthalate film as a base material, and an electron beam (E) using aluminum as a vapor deposition source on the other side on which the printed picture layer is not formed.
B) A 200-nm-thick aluminum oxide vapor-deposited film was formed by a reactive vacuum vapor deposition method while supplying oxygen gas by a heating method. (2). On the other hand, a biaxially oriented polypropylene film having a thickness of 20 μm was prepared. (3). Next, the biaxially stretched polypropylene film and a printed pattern layer formed on one surface and a deposited film of aluminum oxide formed on the other surface having a thickness of 12 μm.
Using the biaxially stretched polyethylene terephthalate film described above, one surface of the former is opposed to the surface of the printed pattern layer, and low-density polyethylene is used between the layers, and is extruded to a thickness of 15 μm. And both were extruded and laminated. (4). Next, a low-density polyethylene was used on the aluminum oxide vapor-deposited film surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the printed pattern layer and the aluminum oxide vapor-deposited film were formed as described above. While extruding this to a thickness of 15 μm, a 20 μm-thick unstretched polypropylene film as a sealant film was extruded and laminated to produce a laminated material according to the present invention.

Embodiment 6 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. First, a desired printing pattern layer was formed on one surface of the film using a gravure ink composition using a gravure printing method. Next, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which a printed pattern layer was formed as described above was used, and was mounted on a delivery roll of a plasma chemical film forming apparatus. 18
A 0 ° silicon oxide thin film layer was formed on the other side of the biaxially stretched polyethylene terephthalate film on which the printed picture layer was not formed. (Plasma chemical film formation conditions) Film formation speed; 100 m / min Plasma power; 10 kW Reaction gas mixture ratio; hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm) Vacuum chamber Degree of vacuum in; 50 μbar (2). On the other hand, a biaxially oriented polypropylene film having a thickness of 20 μm was prepared. (3). Next, a biaxially stretched polypropylene film having a thickness of 20 μm and a printed pattern layer formed on one surface and a silicon oxide thin film layer formed on the other surface were formed to a thickness of 1 μm.
Using a 2 μm biaxially stretched polyethylene terephthalate film, one surface of the former is opposed to the surface of the printed pattern layer, and low density polyethylene is used between the layers and extruded to a thickness of 15 μm. Then, both were extruded and laminated. (4). Next, low-density polyethylene was used on the silicon oxide thin film layer surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the printed pattern layer and the silicon oxide thin film layer were formed as described above. , This is thickness 1
While extruding to a thickness of 5 μm, a non-stretched polypropylene film having a thickness of 20 μm as a sealant film was extruded and laminated to produce a laminate according to the present invention.

Embodiment 7 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. First, a desired printing pattern layer was formed on one surface of the film using a gravure ink composition using a gravure printing method. Next, a 12 μm-thick biaxially stretched polyethylene terephthalate film having a printed pattern layer formed thereon as described above was used and mounted on a delivery roll of a plasma chemical film forming apparatus. 180
The thin film layer of silicon oxide was formed on the other side of the biaxially stretched polyethylene terephthalate film on which the printed picture layer was not formed. (Plasma chemical film formation conditions) Film formation speed; 100 m / min Plasma power; 10 kW Reaction gas mixture ratio; hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm) Vacuum chamber Degree of vacuum in; 50 μbar (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm was used, and an adhesive layer was formed on one surface of the film by a gravure coating method using the following adhesive for laminating. (Laminate adhesive): Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical) (Product name, A-50) (mixing ratio) main agent: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry) (3). Next, a thickness of 20 μm with the above-mentioned adhesive layer was formed.
m, and a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm on which the printed pattern layer and the silicon oxide thin film layer are formed,
The adhesive layer surface of the former and the printed pattern layer surface of the latter were laminated by dry lamination with facing each other. (4). Next, the above laminating adhesive is similarly applied to the silicon oxide thin film layer surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the printed picture layer and the silicon oxide thin film layer formed above are formed. An adhesive layer was formed by coating in the same manner as above, and then a non-stretched polypropylene film having a thickness of 40 μm, which was a sealant film, was used on the surface of the adhesive layer.
Then, a laminated material according to the present invention was manufactured.

Embodiment 8 (1). A 15 μm-thick biaxially stretched nylon film was used. First, a gravure ink composition was used on one side of the film to form a desired printed picture layer using a gravure printing method. next. 15 μm thick with the above printed pattern layer
Of the biaxially stretched nylon film, which was mounted on a delivery roll of a plasma chemical film forming apparatus, and the other side of the biaxially stretched nylon film on which the printed pattern layer was not formed was coated with the following plasma chemistry film. A thin film layer of silicon oxide having a thickness of 160 ° was formed under the film forming conditions to produce a transparent barrier film. (Plasma chemical film formation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 0.8: 3: 3 (unit: slm) Degree of vacuum in vacuum chamber; 50 μbar Cooling / electrode drum supply power: 10 kW (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm was used, and an adhesive layer was formed on one surface of the film using a gravure coating method using the following adhesive for laminating. (Laminate adhesive): Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical) (Product name, A-50) (mixing ratio) main agent: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry) (3). Next, a thickness of 20 μm with the above-mentioned adhesive layer was formed.
m of a biaxially stretched polypropylene film, a 15 μm-thick biaxially stretched nylon film formed with the above-described printed pattern layer and a silicon oxide thin film layer, and the former adhesive layer surface and the latter silicon oxide thin film The layers were dry-laminated with the layers facing each other and laminated. (4). Next, the adhesive for laminating was similarly used on the printed pattern layer surface of a biaxially stretched nylon film having a thickness of 15 μm on which the printed pattern layer and the silicon oxide thin film layer formed above were formed. An adhesive layer is formed by coating, and then, a non-stretched polypropylene film having a thickness of 40 μm, which is a sealant film, is used on the surface of the adhesive layer. The laminated material was manufactured.

Comparative Example 1 (1). Use a roll-up type vacuum evaporator,
A biaxially stretched polyethylene terephthalate film having a thickness of 200 μm is used as a base material, and on one side thereof, aluminum is vapor-deposited by a vacuum vapor deposition method using an electron beam (EB) heating method using aluminum as a vapor deposition source. A film was formed. (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm was used, and a gravure ink composition was used on one surface thereof to form a desired print pattern layer using a gravure printing method. (3). Next, the thickness of the printed pattern layer of 20 μm was formed.
m of a biaxially stretched polypropylene film and a 12 μm-thick biaxially stretched polyethylene terephthalate film on which the above-mentioned aluminum vapor-deposited film is formed. Oppositely, low-density polyethylene was used between the layers, and while extruding it to a thickness of 15 μm, both were extruded and laminated. (4). Next, on the biaxially stretched polyethylene terephthalate film surface of the 12 μm thick biaxially stretched polyethylene terephthalate film having the laminated aluminum vapor-deposited film formed thereon, similarly to the above, using low-density polyethylene, While extruding this to a thickness of 15 μm, a 20 μm-thick unstretched polypropylene film as a sealant film was extruded and laminated to produce a laminated material.

Comparative Example 2 (1). Use a roll-up type vacuum evaporator,
A biaxially stretched polyethylene terephthalate film of μm as a base material, one side of which is subjected to an electron beam (EB) heating method using aluminum as an evaporation source, and a reactive vacuum evaporation method while supplying oxygen gas. Then, a deposited film of aluminum oxide having a thickness of 200 ° was formed. Furthermore, after forming the above-mentioned vapor-deposited film of aluminum oxide, a desired printed picture layer was formed on the vapor-deposited film surface of the aluminum oxide by using a gravure ink composition by a gravure printing method. (2). On the other hand, a biaxially oriented polypropylene film having a thickness of 20 μm was prepared. (3). Next, the biaxially stretched polypropylene film having a thickness of 20 μm and the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm formed with the above-mentioned printed picture layer and a deposited film of aluminum oxide were used. The surface of the printed pattern layer and the surface of the latter were opposed to each other, and low-density polyethylene was used between the layers. While extruding this to a thickness of 15 μm, both were extruded and laminated. (4). Next, a low-density film was formed on the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, on which the printed pattern layer and the aluminum oxide vapor-deposited film were formed, as described above. Using polyethylene, while extruding it to a thickness of 15 μm, extruding and laminating a 20 μm-thick unstretched polypropylene film as a sealant film,
A laminated material was manufactured.

Comparative Example 3 (1). Use a roll-up type vacuum evaporator,
A biaxially stretched polyethylene terephthalate film of μm as a base material, one side of which is subjected to an electron beam (EB) heating method using aluminum as an evaporation source, and a reactive vacuum evaporation method while supplying oxygen gas. Then, a deposited film of aluminum oxide having a thickness of 200 ° was formed. Furthermore, after forming the above-mentioned vapor-deposited film of aluminum oxide, a desired printed picture layer was formed on the vapor-deposited film surface of the aluminum oxide by using a gravure ink composition by a gravure printing method. (2). On the other hand, a biaxially oriented polypropylene film having a thickness of 20 μm was prepared. (3). Next, the biaxially stretched polypropylene film having a thickness of 20 μm and the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm formed with the above-mentioned printed picture layer and a deposited film of aluminum oxide were used. And the surface of the latter biaxially stretched polyethylene terephthalate film are opposed to each other, and low density polyethylene is used between the layers, and while extruding it to a thickness of 15 μm, both are extruded and laminated. did. (4). Next, a low-density polyethylene was used on the printed pattern layer surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the laminated printed pattern layer and the aluminum oxide film were formed as described above. Was extruded to a thickness of 15 μm, and a 20 μm-thick unstretched polypropylene film as a sealant film was extruded and laminated to produce a laminated material.

Experimental Example 1 The following data was measured for each of the laminated materials manufactured in Examples 1 to 8 and Comparative Examples 1 to 3. (1). Measurement of Oxygen Permeability This is for a laminated material at a temperature of 23 ° C. and a humidity of 90% RH.
Under the conditions described above, the measurement was carried out with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA. (2). Measurement of water vapor transmission rate This is for a laminated material at a temperature of 40 ° C. and a humidity of 90% RH.
Under the conditions described above, the measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA. The above measurement results are shown in Table 1 below.

[0042]

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

As is evident from the results shown in Table 1 above, those of Examples 1 to 8 have the same oxygen permeability and water vapor permeability as those of the current product of Comparative Example 1 Degree, and has a water vapor permeability,
Furthermore, it was much better than those of Comparative Examples 2 and 3. This is considered to be such that cracks and the like did not occur in the deposited film of aluminum oxide or silicon oxide constituting the laminated material according to Examples 1 to 8.

[0044]

As is apparent from the above description, according to the present invention, another substrate is laminated on a thin film of an inorganic oxide having a barrier performance without applying external conditions such as heat or pressure. Focusing on that, first, at least the base material film layer, a resin film layer having a deposited film of inorganic oxide, and, in a laminated material obtained by laminating a heat-sealing resin layer, the print pattern layer, In advance, the base film constituting the base film layer, or provided on the non-inorganic oxide deposited film side of the resin film constituting the resin film layer having the inorganic oxide deposited film, and then the base film layer, A resin film layer having an inorganic oxide vapor-deposited film, and a heat-sealing resin layer, for example, extruded between the respective layers by laminating.
Through an extruded resin layer by lamination, to produce a laminated material by laminating, thus, using the laminated material, to manufacture a packaging container of various forms by bag making or box making, Thereafter, the packaging container is filled with various contents to produce packaging products of various forms, and no cracks or the like are observed in the inorganic oxide thin film having a barrier function. Furthermore, no peeling phenomenon or the like is observed in the laminated material constituting the packaging container, and the laminate has an excellent laminating strength and the like, and has a high barrier property against oxygen gas or water vapor. A laminate material useful for filling and packaging various articles such as cosmetics, chemicals, and others, particularly confectionery, snack foods, and the like can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a laminated material according to the present invention.

FIG. 2 is a schematic cross-sectional view illustrating a layer configuration of an example of a laminated material according to another embodiment of the present invention.

FIG. 3 is a schematic configuration diagram of a roll-to-roll vacuum evaporation apparatus illustrating an example of manufacturing an inorganic oxide evaporation film according to the present invention.

FIG. 4 is a schematic configuration diagram of a plasma chemical vapor deposition apparatus illustrating another example of producing a deposited film of an inorganic oxide according to the present invention.

[Explanation of symbols]

 Reference Signs List A laminated material B laminated material 1 base film layer 2 printed picture layer 3 deposited film of inorganic oxide 4 resin film layer 5 heat-sealing resin layer 6 extruded resin layer by extrusion laminating 11 winding vacuum evaporation Apparatus 12 Vacuum chamber 13 Unwinding roll 14 Resin film 15, 16 Guide roll 15 ', 16' Guide roll 17 Cooled coating drum 18 Deposition source 19 Crucible 20 Oxygen outlet 21 Mask 22 Take-up roll -Roll 31 Plasma chemical vapor deposition device 32 Vacuum chamber-33 Unwinding roll 34 Resin film 35 Auxiliary roll 36 Cooling and electrode drum 37, 38, 39 Raw material volatile supply device 40 Raw material supply nozzle 41 Glow discharge plasma 42 Power supply 43 magnet 44 auxiliary roll 45 take-up roll 46 vacuum pump

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 81/34 B65D 81/34 C23C 14/08 C23C 14/08 NF term (Reference) 3E086 AA23 AD01 AD02 BA04 BA15 BA40 BB01 BB22 BB51 BB62 BB87 CA01 CA07 CA28 4F100 AA17B AA19 AK01A AK01B AK01C AK01D AK06G AK07 AK41 BA04 BA07 BA10A BA10C BA15 CB00 EH66B GB15 HB00D JD02 JL12C4K0BA03A02A

Claims (6)

[Claims] 1. A laminated material comprising at least a substrate film layer, a resin film layer having an inorganic oxide vapor-deposited film, and a heat-sealing resin layer. A laminated material provided on a non-inorganic oxide deposited film side of a base film constituting a film layer or a resin film constituting a resin film layer having an inorganic oxide deposited film. 2. A laminated material comprising at least a substrate film layer, a resin film layer having an inorganic oxide vapor-deposited film, and a heat-sealing resin layer, wherein a printed pattern layer is formed of a substrate. A base film constituting the film layer, or a resin film having a deposited inorganic oxide film is provided on the non-inorganic oxide deposited film side of the resin film constituting the resin film layer. A laminated material comprising: a resin film layer having a vapor-deposited material; and a heat-sealing resin layer, which are laminated via an extruded resin layer formed by extruding a laminate. 3. At least a base film layer, a printed pattern layer provided on a base film constituting the base film layer,
A resin film layer having a deposited film of an inorganic oxide, and
3. The laminated material according to claim 1, wherein heat-sealing resin layers are sequentially laminated. 4. A non-inorganic oxide deposited film side of a resin film constituting at least a substrate film layer, a resin film layer having an inorganic oxide deposited film, and a resin film layer having the inorganic oxide deposited film. A printed pattern layer provided on the
3. The laminated material according to claim 1, wherein heat-sealing resin layers are sequentially laminated. 5. The laminated material according to claim 4, wherein the printed picture layer faces the substrate film layer side. 6. The laminate according to claim 4, wherein the printed picture layer faces the heat-sealing resin layer.