JP2002331605A - Barrier type film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier type packaging film useful to fill and package various type articles such as food and drink, pharmaceutical preparations, cosmetics, chemical products, in a boiling or retort treatment manner having a water resistance for a boiling or retort treatment and further having high barrier properties, perfume retentivity or the like for an oxygen gas or a water vapor or the like, even when a polyamide resin film is used as a plastic base. SOLUTION: A barrier type film comprises a water barrier wall film made of a coated film of a resin composition containing a resin as a main component of a vehicle and provided on one surface of the polyamide resin film, and a vapor-deposited thin film of an inorganic oxide provided on the other surface of the polyamide resin film. More particularly, the barrier film comprises the water barrier wall film made of the coated film of the resin composition containing a specific resin made of one or two ore more types selected from the group consisting of a polyester resin, an acrylic resin, a hydrocarbon resin and a silicon resin as a main component of the vehicle provided on the one surface of the polyamide resin film, and the vapor-deposited thin film of the inorganic oxide provided on the other surface of the polyamide resin film. The laminating material using the barrier film is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barrier film and a laminated material using the same, and more particularly, to a film having excellent transparency, barrier properties against oxygen gas or water vapor and the like, and further having laminating suitability. And, for example, food and drink,
The present invention relates to a barrier film useful for filling and packaging various articles such as pharmaceuticals, cosmetics, chemicals, and the like, and particularly to a barrier film useful for boiled or retorted filled packaging and a laminated material using the same.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, etc. in a boiling or retort manner.
Among them, in recent years, as a barrier material against oxygen gas or water vapor, the surface of a plastic substrate such as a polyester resin film or a polyamide resin film has been coated with an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like. Physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, or plasma chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition, etc. A transparent gas barrier film formed by forming a vapor-deposited film of the inorganic oxide by utilizing a chemical vapor deposition method (CVD method) or the like has attracted attention. The transparent gas barrier film described above is laminated with a base material such as another resin film to produce a laminated material,
Using this, a packaging bag is manufactured, and further, the contents are filled and packaged in the packaging bag, and thereafter, the package is subjected to boiling or retort treatment, etc., and is cooked or sterilized by heating. Of packaging products. Thus,
The above-mentioned transparent gas barrier film has excellent transparency as compared with a conventional barrier material made of aluminum foil or polyvinylidene chloride-based resin coat film, and furthermore has a barrier property against oxygen gas, water vapor and the like and a fragrance retention property. It is expected to be highly demanded in the future as a material having a high barrier property, a material having a high barrier property, a material having an appropriate incineration disposal treatment, etc., and being suitable for environmental protection.

[0003]

However, a laminated material is manufactured by laminating another resin film or the like on the transparent gas barrier film, and a packaging bag is manufactured using the laminated material. Even if the contents are filled and packed in a bag, and then the package is subjected to boil or retort treatment to produce a sterilized packaged product, often the lamination of the laminated material constituting the packaging bag Strength is not obtained, for example,
Phenomena such as bag breakage occur, and the gas barrier property against oxygen gas, water vapor, and the like also deteriorates, and it is difficult to produce a sufficiently satisfactory packaged product.
In particular, in a transparent gas barrier film using a polyamide resin film as a plastic substrate,
Compared to a transparent gas barrier film using a polyester resin film or the like as a plastic substrate, the polyamide resin film absorbs water during boiling or retorting because the polyamide resin film has higher water absorption. Or the polyamide-based resin film swells due to adsorption, and thus the inorganic oxide vapor-deposited film lacks the ability to follow the swelling of the polyamide-based resin film. There is a problem that cracks and the like are generated in the oxide deposited film, and gas barrier properties and the like are significantly reduced. Further, in some cases, the polyamide-based resin film as a plastic base material shrinks due to the action of high temperature, high pressure, hot water or the like at the time of boiling or retorting treatment, and thereby, the inorganic oxide deposited film is peeled off. However, there is also a problem that it is dropped and no longer used. For this reason, as described above, in the transparent gas barrier film described above, in order to improve the water resistance of the polyamide resin film as the plastic substrate, one side of the polyamide resin film as the plastic substrate is provided with a water resistant film. A method of laminating another plastic film rich in water resistance and forming a water-resistant layer has been proposed.In this case, another plastic film rich in water resistance, a transparent gas barrier film, and
A packaging material must be manufactured by laminating at least three layers of a film such as a heat-sealing resin film, and the processing steps and the like become complicated, and the obtained packaging material has a thickness greater than a desired thickness. Although it is likely to become thicker, and the effect due to it can be expected as such, there is still a boil or retort treatment suitable, and a retort barrier packaging material having a sufficiently satisfactory high barrier property is provided. The reality is that it is difficult to manufacture. Instead of laminating the above-mentioned other water-resistant plastic film, for example, a resin composition having a water-resistant resin as a main component of the vehicle is prepared, and this is prepared on one side of a polyamide resin film as a plastic substrate. In addition, a method of coating and forming a water-resistant layer with the coating film has been attempted.
Although the effect of the retort can be expected as it is, a retort barrier packaging material having a high barrier property that is still suitable for boiling or retort treatment and has a sufficiently satisfactory high barrier property has been supplied to the market, and It cannot be said that they are being offered to the public. Therefore, the present invention uses a polyamide resin film as a plastic substrate, but has water resistance to boil or retort treatment, and further has high barrier properties against oxygen gas or water vapor, aroma retention, and the like, and , Excellent transparency, for example,
An object of the present invention is to provide a barrier packaging material useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, etc. in a boil or retort manner.

[0004]

In order to solve the above-mentioned problems, the present inventor coated a resin composition on one side of a polyamide resin film as a plastic substrate.
As a result of further various studies on a method of forming a water-resistant layer, a coating film of a resin composition containing a specific resin as a main component of a vehicle has excellent close-adhesion to a polyamide resin film, and Focusing on the fact that the coating film functions as a water barrier film, first, on one surface of the polyamide-based resin film, one or two of a polyester-based resin, an acrylic-based resin, a hydrocarbon-based resin, or a silicon-based resin. Forming a coating film of a resin composition containing a specific resin composed of at least one kind of a vehicle as a main component of a vehicle, and further, on the other surface of the polyamide resin film, a silicon oxide, an evaporated thin film of an inorganic oxide such as aluminum oxide, etc. To produce a barrier film, and further, at least a heat-sealing resin layer is provided on the vapor-deposited thin film surface of the inorganic oxide of the barrier film to produce a laminated material. Then, by using the laminated material, which manufactures bag manufacturing to packaging bags, thereafter, filling packaging contents into 該包 the wearing bag, further, the opening heat - city -
To produce a packaged product, boiled or retorted, heat sterilized or cooked to produce a packaged product, and a specific resin is used as the main component of the vehicle. The coating film has excellent close-adhesion to the polyamide resin film, and further prevents hot water or the like from entering the polyamide resin film during boiling or retorting, functions as a water barrier film, and serves as a water barrier film. Suppress water absorption, swelling, shrinkage, etc.
In addition, the adhesiveness between the surface of the polyamide resin film and the deposited thin film of inorganic oxide is excellent, and as a result, it has an extremely high barrier property against oxygen gas or water vapor and the like, and has excellent transparency, fragrance retention and the like. Excellent, moreover, also excellent in laminate strength, for example, food and drink, pharmaceuticals, cosmetics, chemicals,
The present invention has been completed by finding that a barrier film useful for filling and packaging various other articles such as boil or retort and a laminated material using the same can be produced.

That is, according to the present invention, a water barrier film comprising a coating film of a resin composition containing a resin as a main component of a vehicle is provided on one surface of a polyamide resin film, and an inorganic oxide film is provided on the other surface. , Specifically, on one surface of a polyamide-based resin film, one or more of a polyester-based resin, an acrylic-based resin, a hydrocarbon-based resin, or a silicon-based resin. A water barrier film comprising a coating film of a resin composition containing a specific resin as a main component of a vehicle is provided, and a barrier film characterized by providing a vapor-deposited thin film of an inorganic oxide on the other surface and a barrier film. It relates to the laminated material used.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of a barrier film according to the present invention and a laminated material using the same will be described with reference to the drawings by exemplifying a few examples.
FIGS. 3 and 4 are schematic cross-sectional views showing an example of the layer structure of the barrier film according to the present invention. FIG. 5 is a schematic view showing an example of the layer structure of the laminate according to the present invention. FIG.

First, the barrier film A according to the present invention
As shown in FIG. 1, a water barrier film 2 composed of a coating film of a resin composition containing a resin as a main component of a vehicle, on one surface of a polyamide-based resin film 1, specifically,
The water barrier film 2a made of a coating film of a resin composition containing one or more of a polyester resin, an acrylic resin, a hydrocarbon resin, or a silicon resin as a main component of the vehicle is used. And on the other side,
The basic structure is that it has a configuration in which a deposited thin film 3 of an inorganic oxide is provided. As a specific example of the barrier film according to the present invention, as shown in FIG. 2, as shown in FIG. The barrier film 2, specifically, one of a polyester-based resin, an acrylic-based resin, a hydrocarbon-based resin, or a silicon-based resin
Water barrier film 2a composed of a coating film of a resin composition containing, as a main component of the vehicle, a specific resin composed of one or more species
And a barrier film A having a configuration in which one or two or more multilayer films (not shown) of the inorganic oxide vapor-deposited thin film 3a formed by chemical vapor deposition are provided on the other surface.
_One can be mentioned. Next, as another specific example of the barrier film according to the present invention, as shown in FIG. 3, a resin composition containing a resin as a main component of a vehicle is provided on one surface of a polyamide resin film 1. The water barrier film 2 composed of a coating film, specifically, a specific resin composed of one or more of a polyester-based resin, an acrylic-based resin, a hydrocarbon-based resin, or a silicon-based resin is used as a main component of the vehicle. A water barrier film 2a made of a coating film of a resin composition to be formed is provided, and one or two or more multilayer films (not shown) of an inorganic oxide vapor-deposited thin film 3b formed by physical vapor deposition are provided on the other surface. not) can be mentioned barrier film a ₂ having the configuration in which a. Further, as another specific example of the barrier film according to the present invention, as shown in FIG. 4, on one surface of the polyamide-based resin film 1, a resin composition containing a resin as a main component of a vehicle is used. The water barrier film 2 composed of a coating film, specifically, a polyester resin, an acrylic resin, a hydrocarbon resin,
Alternatively, a water barrier film 2a composed of a coating film made of a resin composition containing a specific resin composed of one or more silicon-based resins as a main component of a vehicle is provided. A vapor-deposited inorganic oxide thin film 3a is provided by a growth method, and an inorganic oxide vapor-deposited thin film 3b is provided on the inorganic oxide vapor-deposited thin film 3a by a physical vapor deposition method. 3a, can be mentioned barrier film a ₃ having the configuration in which a multi-layered film 4 made 3b.

Next, in the present invention, an example of the laminated material S using the barrier film according to the present invention will be exemplified. In the example using the barrier film A shown in FIG. As shown in FIG. 5, if necessary, a desired printed pattern layer 5 is provided on the surface of the inorganic oxide thin film 3 of the barrier film A shown in FIG. 1, and the printed pattern layer 5 is further included. At least a heat-sealing resin layer 6 is provided on the entire surface. In the drawings, reference numerals 1, 2, 2a, etc. have the same meaning as described above.
The above examples illustrate only a few examples of the barrier film according to the present invention and the laminated material using the same, and the present invention is not limited thereto. For example, although not shown, in the above-described laminated material, the contents to be filled and packaged, depending on the purpose of use, other plastic films, paper base materials, and the like,
The laminated material can be manufactured by arbitrarily laminating it at a desired position.

Next, in the present invention, the material, material, manufacturing method and the like constituting the barrier film and the laminated material according to the present invention will be described. First, in the present invention, the polyamide resin film is For example, nylon 46, nylon 6, nylon 66, nylon 61, which can satisfy the strength and heat resistance as a packaging material for boiling or retorting, particularly, suitability for retorting or boiling treatment.
Various polyamide-based resins such as N.0, nylon 612, nylon 11, nylon 12, and others can be used, and a polyamide-based resin film or sheet obtained by forming a film thereof can be used. Specifically, using the polyamide resin described above, for example, using one or more of the above resins, using the film forming method such as inflation method, T-die method, and the like, A method of forming a resin alone, or a method of forming a multilayer co-extrusion film using two or more different resins, and a method of mixing two or more resins before forming a film. A film or sheet of a polyamide resin is produced by a method of forming a film, and the film is further formed in a uniaxial or biaxial direction by using, for example, a tenter method or a tuber method. A stretched polyamide resin film or sheet can be used. The thickness of the above-mentioned biaxially stretched polyamide resin film or sheet is appropriately set based on the stability at the time of production of the film or sheet, the stability at the time of boiling and retorting, and the like. Although it is possible to do about 10 to 100 μm, preferably 15 to 50 μm
The m-th position is desirable. In the above, when forming a polyamide resin, for example, the processability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release, flame retardant, For the purpose of improving and modifying the antifungal property, the electrical properties, etc., various plastic compounding agents and additives can be added.
From a very small amount to several tens%, it can be arbitrarily added according to the purpose. Further, in the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, A fungicide, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the polyamide resin film or sheet may be subjected to, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge A pretreatment such as a treatment, an oxidation treatment using a chemical agent, or the like, or the like can be arbitrarily performed. The above surface pretreatment may be performed in a separate step before forming a water barrier film composed of a coating film of a resin composition containing a specific resin as a main component of a vehicle, or a deposited thin film of an inorganic oxide. In addition, the water barrier film composed of the above-mentioned coating film, or a pretreatment for forming a vapor-deposited thin film of an inorganic oxide can be performed in a pretreatment by an inline treatment, and in such a case, the manufacturing cost is reduced. There is an advantage that can be. The above surface pretreatment is performed as a method for improving the adhesion between a water barrier film composed of a polyamide resin film and a coating film, or a deposited thin film of an inorganic oxide. In addition, as a method of improving, for example, in advance, a primer-co
Agent layer, undercoat agent layer, or vapor deposition anchor
A coating agent layer and the like can be arbitrarily formed. As the coating agent layer for the above pretreatment, for example, a resin composition containing a polyester-based resin, a polyurethane-based resin, or the like as a main component of the vehicle can be used. In the above, as a method for forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. Method, a kiss coating method, a coating method such as other methods, and the coating time may be set as a post-process after the biaxial stretching of the polyamide resin film, or
It can be carried out by in-line processing of biaxial stretching processing or the like. In the present invention, specifically, it is preferable to use a biaxially stretched nylon film or the like.

Next, in the present invention described above, a transparent barrier film according to the present invention and a water barrier film comprising a coating film of a resin composition containing a resin constituting a laminate as a main component of a vehicle, Has a polyester resin,
A water barrier film composed of a resin composition containing a specific resin composed of one or more of an acrylic resin, a hydrocarbon resin, or a silicon resin as a main component of a vehicle will be described. As the barrier film, for example, a polyester-based resin, an acrylic-based resin, a hydrocarbon-based resin, or a specific resin composed of one or more silicon-based resins as a main component of the vehicle, and further,
If necessary, for example, fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc. One or more additives are arbitrarily added, and a solvent-type, aqueous-type, or emulsion-type resin composition obtained by sufficiently kneading with a solvent, a diluent, or the like is prepared. Using the resin composition, for example, a roll coat method, a gravure roll coat method, a knife coat method, a spray coat method,
Coating method such as kiss roll coating method, squeeze roll coating method, reverse roll coating method, curtain flow coating method, etc., or offset printing, gravure printing, It is coated or printed using a printing method such as silk screen printing, transfer printing, etc., and then subjected to heat drying and further aging treatment to give a film thickness of, for example, 0.1 g / m ² ~10g / m ² (dry state) position, the preferably form a 0.5g / m ² ~5g / m ² coating or printing film made of (dry) of the coating film according to the present invention Water barrier film can be formed.

In the above, examples of the polyester resin include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, and polypropylene glycol. , Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, neopentyl glycol, cyclohexanedimethanol 2.2-bis (4 '-. Beta.-hydroxyethoxyphenyl) propane, naphthalene One or more polyhydric alcohols such as diol and others, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, naphthalenedicarboxylic acid, maleic acid, One kind of polybasic acids such as fumaric acid, adipic acid and others It can be used a polyester resin obtained by polycondensation of a stone more. Specifically, for example, polyethylene terephthalate resin,
Various polyester resins such as polyethylene isophthalate resin, polytetramethylene isophthalate resin, maleic acid resin, aliphatic polyester resin, unsaturated polyester resin, and others can be used. Examples of the above-mentioned polyacrylic resin include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, etc., alkyl esters of these unsaturated carboxylic acids, and the like. Polymers obtained by polymerizing one or more monomers such as acid amides, nitriles, and others, and polymers obtained by adding other monomers to the monomers and polymerizing them. can do. Specifically, for example, various acrylic resins such as polyethyl acrylate, polyethyl methacrylate, polymethyl methacrylate, polyacrylonitrile, thermosetting acrylic resins, and others can be used. Next, as the hydrocarbon resin, for example, polyethylene resin, polypropylene resin, polystyrene resin, polybutadiene resin, polyisoprene resin, terpene resin, cumarone-indene resin, petroleum resin, cyclo resin A pentadiene resin or the like can be used. Next, as the silicon-based resin, for example, methyl polyorganosiloxane, methyl ethyl polyorganosiloxane, silicone resin,
Modified silicone resin, etc. can be used.

Thus, in the present invention, the above-mentioned specific resin has, for example, a resin having a close adhesiveness and an affinity with a polyamide resin film from various synthetic resins. When a coating film of the composition is provided on a polyamide-based resin film, both of them are firmly and closely adhered, and further, using a chemical vapor deposition method, or a physical vapor deposition method or the like, silicon oxide, When forming a deposited thin film of an inorganic oxide such as aluminum oxide, the deposition conditions at that time,
For example, select a resin that is resistant to high-temperature heat, oxygen gas, active species, etc., and has the property of being durable in chemical, physical, etc., capable of forming a tough coating film. It can be used.

Next, in the present invention, the transparent barrier film according to the present invention and the vapor-deposited thin film of an inorganic oxide constituting a laminate or the like will be described. For example, a chemical vapor deposition method (Chemical VaporDe) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
A deposition thin film of an inorganic oxide can be formed by a method such as a position method or a CVD method. In the present invention, specifically, on the other surface of the polyamide resin film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. In addition, a vapor-deposited thin film of an inorganic oxide such as silicon oxide is formed by using a plasma enhanced chemical vapor deposition (CVD) method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. can do. In the above, as the low-temperature plasma generator, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma or the like can be used, and thus,
In the present invention, in order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method for forming a vapor-deposited thin film of an inorganic oxide by the above-mentioned plasma enhanced chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a plasma enhanced chemical vapor deposition apparatus showing an outline of a method for forming a deposited thin film of a substance. As shown in FIG. 5 described above, in the present invention, the vacuum chamber-1 of the plasma enhanced chemical vapor deposition apparatus 11 is used.
A polyamide resin film 2 having a water barrier film composed of a coating film made of a resin composition containing a specific resin as a main component of a vehicle is fed out from an unwinding roll 13 disposed in the inside of the roll 2, and further, the polyamide resin The film 2 is conveyed on the peripheral surface of the cooling / electrode drum 15 at a predetermined speed via the auxiliary roll 14. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatile supply device 18 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and was transported onto the peripheral surface of the cooling / electrode drum 15 described above. Plasma is generated on the other surface of the polyamide-based resin film 2 by the glow discharge plasma 20, which is irradiated to form a deposited thin film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at that time,
A predetermined power is applied to the electrode drum 15 from a power source 21 disposed outside the chamber, and a magnet 22 is disposed near the cooling / electrode drum 15 to promote generation of plasma. Then, the polyamide resin film 2 having the above-mentioned vapor-deposited thin film of an inorganic oxide such as silicon oxide formed on the other surface is wound up on a winding roll 24 via an auxiliary roll 23, According to the present invention, it is possible to produce a deposited thin film of an inorganic oxide by a plasma enhanced chemical vapor deposition method. In the figure, 25 is
Represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby.

In the above, a monomer for vapor deposition of an organic silicon compound or the like forming a vapor deposited thin film of an inorganic oxide such as silicon oxide.
As the gas, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, Phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the above-mentioned organosilicon compounds, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its characteristics and the like. In the above description, as the inert gas, for example, argon gas, helium gas, or the like can be used.

In the present invention, the silicon oxide vapor-deposited thin film formed as described above undergoes a chemical reaction between a monomer gas such as an organic silicon compound and oxygen gas, and the reaction product is formed on the other surface of the polyamide resin film. Tightly adhered to
It is capable of forming a thin film having high flexibility and the like, and is usually a continuous vapor-deposited thin film mainly composed of silicon oxide represented by a general formula SiO _x (where X represents a number of 0 to 2). . Thus, from the viewpoint of transparency, barrier properties, and the like, the silicon oxide vapor-deposited thin film has the general formula SiO _x (where X is
Represents a number from 1.3 to 1.9. It is preferable that the thin film is mainly composed of a silicon oxide deposited film represented by the formula (1). In the above, the value of X changes depending on the molar ratio between the monomer gas and the oxygen gas, the energy of the plasma, and the like.
Generally, as the value of X decreases, the gas permeability decreases, but the film itself becomes yellowish and the transparency deteriorates. Further, the above-mentioned deposited thin film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or both elements Is contained as a trace constituent element, and the thickness thereof is in the range of 50 ° to 500 °, and the constituent ratio of the essential constituent element and the trace constituent element is in the thickness direction. It is changing continuously. Further, when the silicon oxide vapor-deposited thin film contains a compound made of carbon, the carbon content is reduced in the depth direction of the film thickness. Thus, in the present invention, the above-mentioned vapor-deposited thin film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xray).
Photoelectron Spectrosco
py, XPS), secondary ion mass spectrometer (Secon
dary Ion Mass Spectroscop
y, SIMS), etc. to confirm the above physical properties by performing elemental analysis of the deposited silicon oxide thin film using a method of analyzing by ion etching in the depth direction, etc. using a surface analyzer such as Is what you can do. Further, in the present invention, the thickness of the deposited silicon oxide thin film is desirably about 1000 以下 or less, and more desirably 500 、 or less.
0-500 °, more preferably 100-300 °, and thus, in the above, 300 °,
If the thickness is more than 500 °, furthermore, 1000 °, it is not preferable because cracks and the like are easily generated in the film, and if it is less than 100 °, furthermore, less than 50 °, it is difficult to exhibit the barrier effect. It is undesirable. In the above description, the film thickness is determined, for example, by a fluorescent X-ray analyzer (model name, RIX200 manufactured by Rigaku Corporation).
(Type 0) and can be measured by a fundamental parameter method. Further, in the above, as means for changing the thickness of the deposited silicon oxide thin film, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down. In general, it is preferable to form a deposited film at a deposition rate of 50 to 200 n / min.

Further, in the present invention, the barrier film according to the present invention or the vapor-deposited thin film of an inorganic oxide constituting the laminated material will be described. Physical vapor deposition methods such as sputtering and ion plating (P
physical Vapor Deposition
, PVD method) to form a vapor-deposited thin film of an inorganic oxide. In the present invention, specifically, a metal oxide is used as a raw material, and the metal oxide or the metal oxide is used as a raw material, or a vacuum evaporation method in which the metal oxide is heated and vapor-deposited on the other surface of the polyamide resin film. A vapor-deposited film is formed using an oxidation-reaction deposition method in which oxygen is introduced and oxidized to deposit on the other surface of the polyamide resin film, and a plasma-assisted oxidation-reaction deposition method in which the oxidation reaction is further promoted by plasma. be able to. In the present invention, a specific example of a method for forming a thin film of an inorganic oxide by a physical vapor deposition method is shown in FIG. 6. FIG. 6 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 6, the vacuum chamber-5 of the take-up type vacuum evaporation apparatus 51
2, the polyamide-based resin film 2 having a water barrier film composed of a resin composition containing a specific resin fed out of the unwinding roll 53 as a main component of the vehicle is formed by a guide roll 54, 55. Via the cooling drum 56. Thus, the above cooled core
On the other surface of the polyamide-based resin film 2 guided on the heating drum 56, the evaporation source 58 heated by the crucible 57, for example, metal aluminum or aluminum oxide is evaporated. Oxygen gas or the like is ejected from the gas outlet 59, and while supplying the same, through the masks 60 and 60, for example, a deposited thin film of an inorganic oxide such as aluminum oxide is formed. A polyamide resin film 2 having a vapor-deposited thin film of an inorganic oxide such as aluminum oxide formed on the other surface is fed out through guide rolls 55 'and 54', and then wound up on a take-up roll 61. Thereby, a deposited thin film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention.

In the above, as the thin film of the inorganic oxide, any thin film on which a metal oxide is basically deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg) , Calcium (C
a), potassium (K), tin (Sn), sodium (N
a) A vapor-deposited thin film of an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. Thus, as a material suitable for a packaging material and the like, a vapor-deposited thin film of an oxide of a metal such as silicon (Si) and aluminum (Al) can be given. Thus, the above-described vapor-deposited thin film of a metal oxide can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. The notation is, for example, SiO _x , AlO _x , MO _X (However, as such MgO _X, wherein, M represents a metal element,
The range of the value of X differs depending on the metal element. ). Further, as the range of the value of X, silicon (Si) is 0 to 2 and aluminum (Al)
Is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 1.
0.5, tin (Sn): 0-2, sodium (Na)
Is 0 to 0.5, boron (B) is 0 to 1, 5, titanium (Ti) is 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, yttrium. (Y) is 0 to
Values can be in the range of 1.5. In the above,
When X = 0, it is a perfect metal, 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, packaging materials generally include silicon (Si) and aluminum (A).
Except for l), the examples used are poor and silicon (Si)
Is 1.0 to 2.0, and aluminum (Al) is 0.5
A value in the range of ~ 1.5 can be used. 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 used, but is, for example, about 50 to 2000 °, preferably about 100 to 1000 °. It is desirable to select and form arbitrarily within the range. In the present invention, the inorganic oxide vapor-deposited thin film is not limited to one layer of the inorganic oxide vapor-deposited thin film, but may be a laminate of two or more layers. Alternatively, as the metal oxide, one kind or a mixture of two or more kinds may be used to form a thin film of an inorganic oxide mixed with different materials.

Further, in the present invention, the barrier film according to the present invention or the vapor-deposited thin film of the inorganic oxide constituting the laminated material includes the above-mentioned chemical vapor deposition method,
By using the physical vapor deposition method together, a vapor-deposited inorganic oxide thin film composed of a multilayer film of two or more layers of the vapor-deposited inorganic oxide thin film can be formed by both methods. Thus, in the present invention, as the above-mentioned inorganic oxide deposited thin film, first,
A dense, highly flexible inorganic oxide deposited thin film is provided by chemical vapor deposition, and then an inorganic oxide deposited thin film is deposited on the inorganic oxide deposited thin film by physical vapor deposition. It is desirable to form a multilayer film of two or more layers in which cracks and the like are prevented from occurring. In the present invention, on the surface of the above-described inorganic oxide vapor-deposited thin film, on the vapor-deposited inorganic oxide thin film, when further laminating another substrate, its close adhesion, affinity In order to improve the like, for example, using an inert plasma gas or the like containing an oxygen gas, etc. on the evaporated thin film surface of the inorganic oxide, plasma discharge treatment to form a plasma treated surface, or corona discharge treatment To form a corona treated surface or the like.

Next, in the present invention, as a print pattern layer constituting the laminated material according to the present invention, for example, a usual gravure ink composition, offset ink composition, Using a letterpress ink composition, a screen ink composition, and other ink compositions, for example, a gravure printing method, an offset printing method,
Use letterpress printing method, silk screen printing method, other printing methods such as characters, figures, pictures, symbols,
It can be configured by forming a desired print pattern made of other materials. Thus, in the present invention, one or more of the above-mentioned vehicles are used as a main component,
To this, one or more kinds of coloring agents such as dyes and pigments are added, and if necessary, for example, a light stabilizer such as a filler, a stabilizer, a plasticizer, an antioxidant, and an ultraviolet absorber; Ink composition in various forms obtained by arbitrarily adding additives such as dispersant, thickener, desiccant, lubricant, antistatic agent, crosslinking agent, etc., and kneading with a solvent, diluent, etc. Can be used.

Next, in the present invention, a heat sheet constituting a laminated material using the barrier film according to the present invention.
As the heat-sealing resin forming the conductive resin layer, a resin film or sheet that can be melted by heat and fused to each other can be used. Polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer
Resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene 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 the form of a coating film made of a composition containing the resin. The thickness of the film or film or sheet is 5
μm to 300 μm, more preferably 10 μm
m to 100 μm is desirable.

In the present invention, in addition to the heat-sealing resin layer as described above, examples of the laminated material according to the present invention include various resin films, paper base materials, metal materials, and synthetic materials. Various kinds of laminated materials can be manufactured by optionally combining with packaging materials constituting packaging containers such as paper, cellophane, etc., and a packaging material suitable for filling and packaging various articles that can be boiled or retorted. It can be manufactured. As the resin film, 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, acid-modified polyolefin resin, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin , Polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylnitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene- Styrene copolymer (AB Resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluororesin, diene resin, polyacetal resin Any known resin film or sheet such as resin, polyurethane resin, nitrocellulose, etc. can be used. In the present invention, the film or sheet is unstretched,
Any of those stretched in uniaxial or biaxial directions can be used. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film. Further, in the above, as the paper substrate, for example, a paper substrate such as a strongly sized bleached or unbleached paper, a paper substrate such as pure white roll paper, kraft paper, paperboard, or processed paper, or the like is used can do. In the above, as the paper base material constituting the paper layer, it is desirable to use a base material having a basis weight of about 80 to 600 g / m ² , preferably a base weight of about 100 to 450 g / m ² . Further, in the above, as the metal material, for example, aluminum foil, or
A resin film having an aluminum evaporated film or the like can be used.

Next, a method of manufacturing a laminated material using the above-mentioned materials in the present invention will be described. As the method, a usual packaging material is laminated.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pre-treatment such as a corona treatment, an ozone treatment, a framing treatment, or the like can be performed on the film. Anchor coating agents such as polyester, isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate And known adhesives such as adhesives for laminates such as cellulose, cellulose, etc.
Coating agents, adhesives and the like can be used.

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using a laminated material manufactured by such a method, the heat-sealing resin layer of the inner layer is made to face the surface, and it is folded or the two sheets are overlapped, and furthermore, the peripheral edge portion is formed. A bag can be formed by providing a seal portion by heat sealing. Thus, as a bag-making method, the above-mentioned composite film is folded with its inner layer facing the surface, or the two films are overlapped, and the peripheral edge of the outer periphery is further sealed with, for example, a side sheet. Seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seal type),
Heat seals such as pleated seal type, flat bottom seal type, square bottom seal type, etc., to form packaging containers of various forms according to the present invention. Can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) and the like can be manufactured. In the present invention, a tube container and the like can be manufactured using the above-described composite film. In the above, heather
As a method of sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal
And a known method such as an ultrasonic seal.
In the present invention, the packaging container as described above includes, for example, a one-piece type, a two-piece type,
Other spouts or zippers for opening and closing can be arbitrarily attached.

Next, in the case of a liquid-filled paper container containing a paper base as the packaging container, for example, as a laminating material, a laminate in which paper bases are laminated is manufactured, and a desired paper container is manufactured therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head and the like are manufactured using the blank plate to manufacture, for example, a liquid paper container of a brick type, a flat type or a gable-top type. be able to. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

In the present invention, the packaging container produced as described above is excellent in transparency, gas barrier properties against oxygen, water vapor, etc., impact resistance, and the like.
Having post-processing suitability such as printing, bag making or box making,
In addition, preventing the peeling of the thin film of the inorganic oxide as a barrier film, and preventing the occurrence of thermal cracks, preventing its deterioration, exhibit excellent resistance as a barrier film,
For example, food and drink, pharmaceuticals, detergents, shampoos, oils,
It is excellent in filling and packaging suitability, preservation suitability, etc. of various articles such as chemicals or cosmetics such as toothpaste, adhesives and adhesives, and others. In particular, in the packaging material according to the present invention, the packaging bag produced by using the same is filled with the contents from the opening thereof, and then the opening is sealed with a heat seal or the like. Then, the package is manufactured, and then the package is placed in, for example, a retort pot and retorted at 120 ° C. for 30 minutes to produce a retorted (sterilized) packaged product. is there. Further, using the laminated material according to the present invention, the contents are filled and packaged in the same manner as described above in a packaging bag formed by bag making, and a package is manufactured. For 30 minutes to produce a package product heat-sterilized.

[0028]

Next, the present invention will be described in more detail with reference to examples of the present invention. Example 1 (1). 10 parts by weight of polyethylene terephthalate resin was mixed with toluene: methyl ethyl ketone: ethyl acetate = 2: 2:
The resin composition was prepared by dissolving in 90 parts by weight of a mixed solvent consisting of 1 and a polyurethane resin and an isocyanate curing agent in a ratio of 10 parts by weight of the same solvent to 1 part by weight of the resin. The primer solution was prepared. Next, as a base material, a 15 μm-thick biaxially stretched nylon film (manufactured by Toyobo Co., Ltd., product surface, N-1102) was used, and the above-mentioned primer solution was first coated on one surface with a gravure roll. Coating and drying by a coating method to a film thickness of 0.4 μm
(Dry state) A primer layer is formed, and then the above resin composition is coated on the primer layer by gravure roll coating.
And then dried to a film thickness of 1 μm.
A water barrier film consisting of a coating film was formed. (2). Next, the biaxially stretched nylon film on which the water barrier film was formed was fed out of the plasma chemical film forming apparatus.
A mixed gas consisting of hexamethyldisiloxane, oxygen gas, and helium is introduced, plasma is generated by a high frequency of 40 KHZ, and the other surface (non-water barrier film surface) of the biaxially stretched nylon film is A thin film of silicon oxide having a thickness of 150 ° was formed under the following plasma chemical film formation conditions to produce a barrier film according to the present invention. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 3: 1: 3 (unit: slm, standard
Doritter Minute, standard lit
er minute, the same applies hereinafter) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 6.0 × 10 ⁻³ mbar Cooling / electrode drum supply power: 10 kW Film transport speed: Next, the surface of the silicon oxide thin film of the barrier film produced above was subjected to a plasma treatment under the following conditions. as a result,
The surface tension of the silicon oxide thin film surface is from 35 dyn to 62
dyn, and the wettability was improved. Plasma supply power: 3 kW Plasma gas: Mixed gas of helium (He) and oxygen (O ₂ ) (3). Next, using a gravure printing machine on the plasma-treated surface of the deposited silicon oxide thin film of the barrier film,
Using the gravure ink composition, a desired multicolor printed pattern layer was formed. Then, the printed pattern layer 2 was formed as described above.
The axially stretched nylon film is mounted on a first delivery roll of a dry laminating machine, and a two-component curable polyurethane-based laminating adhesive is applied to the printed pattern layer surface by a gravure roll coating method. The composition was applied at a rate of 0.5 g / m ² (dry weight) to form a laminate adhesive layer. Thereafter, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer,
A laminate according to the present invention was manufactured.

Embodiment 2 (1). A resin composition was prepared by dissolving 10 parts by weight of a silicone resin in 90 parts by weight of a mixed solvent of toluene: methyl ethyl ketone = 1: 1, and a polyurethane resin and an isocyanate curing agent were added to 1 part by weight of the resin. On the other hand, a primer solution was prepared by mixing 10 parts by weight of the same solvent as described above. Next, as a substrate, a biaxially stretched nylon film having a thickness of 15 μm (manufactured by Toyobo Co., Ltd., product surface, N-11)
02), the above-mentioned primer solution is first applied to one surface thereof by a gravure roll coating method and dried to form a 0.4 μm-thick (dry state) primer layer. On the primer layer, the above resin composition is coated by a gravure roll coating method.
After drying, a water barrier film composed of a coating film having a thickness of 1 μm was formed. (2). Next, the biaxially stretched nylon film on which the water barrier film was formed was fed out of a take-up type vacuum evaporation apparatus.
It is mounted on a coating drum and fed out onto a coating drum. Under the following conditions, using aluminum as an evaporation source and supplying oxygen gas, a reactive vacuum evaporation method using an electron beam (EB) heating method is used. The other surface (non-water barrier film surface) of the biaxially stretched nylon film has a thickness of 30
A barrier film according to the present invention was manufactured by forming a 0 ° aluminum oxide deposited thin film. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Next, the plasma-treated surface was formed on the surface of the above-prepared barrier film on which the aluminum oxide was deposited by the plasma treatment in the same manner as in (2) of Example 1 described above. (3). Next, using a gravure printing machine, a desired multicolor printed picture layer was formed on the vapor-deposited thin film of aluminum oxide of the barrier film using a gravure ink composition. Next, the biaxially stretched nylon film having the printed picture layer formed thereon is mounted on a first delivery roll of a dry laminating machine, and a two-component curing type is applied to the printed picture layer surface using a gravure roll coating method. Polyurethane Lamine-
The adhesive for coating was applied at a rate of 4.5 g / m ² (dry weight) to form an adhesive layer for laminate. Thereafter, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer for laminating, thereby producing a laminated material according to the present invention.

Embodiment 3 (1). A resin composition is prepared by dissolving 10 parts by weight of a thermosetting acrylic resin in 90 parts by weight of a mixed solvent of toluene: methyl ethyl ketone: ethyl acetate = 2: 2: 1, and a polyurethane resin and an isocyanate curing agent. Was mixed with 1 part by weight of the resin at a ratio of 10 parts by weight of the same solvent as above to prepare a primer solution. Next, as a base material, a 15 μm-thick biaxially stretched nylon film (manufactured by Toyobo Co., Ltd., product surface, N-1102) was used.
It is applied by a coating method and dried to form a primer layer having a thickness of 0.4 μm (dry state).
On the layer, the above resin composition was coated by a gravure roll coating method, and then dried to form a 1 μm-thick water barrier film composed of a coating film. (2). Next, using the biaxially stretched nylon film on which the water barrier film was formed as described above, this was mounted on the delivery roll of the plasma enhanced chemical vapor deposition apparatus in the same manner as in (2) of Example 1 above. Then, a deposited thin film of silicon oxide having a thickness of 150 ° was formed on the other surface (non-water barrier film surface) of the above-mentioned biaxially stretched nylon film. Next, using the biaxially stretched polypropylene film on which the silicon oxide vapor-deposited thin film was formed as described above, in the same manner as in (2) of Example 2 above, this was fed to the delivery roll of a take-up type vacuum vapor deposition apparatus. It is mounted on a coating drum, and is fed out onto a coating drum. Using aluminum as a deposition source and supplying oxygen gas, the above-mentioned silicon oxide is prepared by a reactive vacuum deposition method using an electron beam (EB) heating method. A 300 ° -thick aluminum oxide vapor-deposited thin film was formed on the silicon oxide vapor-deposited thin film of the biaxially stretched nylon film on which the vapor-deposited thin film was formed. (3). Next, using a gravure printing machine, a gravure ink composition is used to coat a desired multicolor printed pattern layer on the aluminum oxide deposited thin film surface of the biaxially stretched nylon film on which the above-described animinium oxide deposited thin film is formed. Was formed. Next, the biaxially oriented polypropylene film having the printed pattern layer formed thereon is mounted on a first delivery roll of a dry laminating machine, and a gravure roll is formed on the printed pattern layer surface.
A two-component curable polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry weight) using a coating method to form a laminating adhesive layer. Next, a non-stretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer for laminating to produce a laminated material according to the present invention.

Embodiment 4 (1). 10 parts by weight of a terpene resin is dissolved in 90 parts by weight of a mixed solvent consisting of toluene: methyl ethyl ketone: ethyl acetate = 2: 2: 1 to prepare a resin composition, and a polyurethane resin and an isocyanate curing agent are mixed with resin 1 A primer solution was prepared by mixing 10 parts by weight of the same solvent as described above with respect to parts by weight. Next, as a substrate, a thickness of 15 μm
m of a biaxially stretched nylon film (manufactured by Toyobo Co., Ltd., N-1102), and the above-mentioned primer solution is first applied to one surface by a gravure roll coating method and dried. Then, a primer layer having a thickness of 0.4 μm (dry state) is formed, and then the above resin composition is coated on the primer layer by a gravure roll coating method, and then dried. Then, a water barrier film composed of a coating film having a thickness of 1 μm was formed. Hereinafter, a barrier film and a laminated material according to the present invention were manufactured in exactly the same manner as in Example 1 described above.

Example 5 In (3) of Example 1 described above, a 70 μm thick low-profile film was formed on the surface of a printed pattern layer of a biaxially stretched nylon film having a printed pattern layer formed thereon via a laminating adhesive layer. Instead of dry laminating a high density polyethylene film to produce a laminated material, a biaxially stretched nylon film having a printed picture layer formed thereon is mounted on a first delivery roll of an extruding laminating machine, and the printed picture layer is formed. A low-density polyethylene film having a thickness of 70 μm was extruded and laminated while being melt-extruded to a thickness of 20 μm using a low-density polyethylene for melt extrusion on the surface. Similarly, a barrier film and a laminate according to the present invention were produced.

Comparative Example 1 (1). As a base material, a biaxially stretched nylon film having a thickness of 15 μm was used, which was mounted on a delivery roll of a plasma chemical film forming apparatus, and the following plasma chemical film forming conditions were applied to the surface of the biaxially stretched nylon film. To form a thin film of silicon oxide with a thickness of 150 ° to produce a barrier film. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 3: 1: 3 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Vapor deposition chamber Degree of vacuum inside: 6.0 × 10 ⁻³ mbar Cooling / electrode drum supply power: 10 kW (2). Next, a plasma-treated surface was formed on the surface of the silicon oxide thin film of the barrier film produced above in exactly the same manner as in Example 1 above. Next, a laminated material was manufactured in exactly the same manner as in Example 1 above, using the barrier film subjected to the plasma treatment.

Comparative Example 2 (1). The following 10 parts by weight of each resin shown in (a) to (b) were mixed with toluene: methyl ethyl ketone: ethyl acetate = 2:
Each resin composition was prepared by dissolving it in 90 parts by weight of a 2: 1 mixed solvent.
A curing agent was mixed with 1 part by weight of the resin at a ratio of 10 parts by weight of the same solvent as above to prepare a primer solution. Next, as a base material, a 15 μm-thick biaxially stretched nylon film (manufactured by Toyobo Co., Ltd., product surface, N-1102) was used, and the above-mentioned primer solution was first coated on one surface with a gravure roll. Coating and drying by a coating method to form a primer layer having a thickness of 0.4 μm (dry state), and then applying each of the above resin compositions on the primer layer by a gravure roll coating method. Coating and then drying were performed to form each water barrier film composed of a coating film having a thickness of 1 μm. (2). Next, using each biaxially stretched nylon film on which the water barrier film was formed as described above, the other surface of the biaxially stretched nylon film (non-water On the barrier film surface), a deposited thin film of silicon oxide is formed to produce each barrier film, and then the silicon oxide thin film surface of each of the produced barrier films is completely replaced with the above-mentioned Example 1. A plasma-treated surface was formed in the same manner, and each laminated material was manufactured in exactly the same manner as in Example 1 above, using the barrier film subjected to the plasma treatment. (I). Ethylene-vinyl alcohol copolymer resin (b). Polyvinyl alcohol resin

EXPERIMENTAL EXAMPLE 1 The following data were measured for each of the barrier films and the laminates produced in Examples 1 to 5 and Comparative Examples 1 and 2 above. (1). Oxygen permeability measurement This is the barrier film and, for the laminate,
The measurement was carried out under the conditions of a temperature of 23 ° C. and a humidity of 90% RH with a measuring device (model name, OXTRAN) manufactured by MOCON, USA. (2). Measurement of water vapor permeability This is a barrier film and, for a laminate,
The measurement was carried out under the conditions of a temperature of 40 ° C. and a humidity of 90% RH with a measuring device (model name, PERMATRAN) manufactured by MOCON, USA. (3). Boil aptitude evaluation This involves using a laminated material, heat-sealing the heat-sealing resin layer surfaces, heat-sealing the outer peripheral edge of the heat-sealing resin layer to produce a packaging bag, and placing the inside of the packaging bag. The contents are filled through the opening, and then the opening is sealed to produce a package. The package is placed in water at 90 ° C., which is a boiling condition, for 30 minutes.
After being immersed for a minute and boiled, the laminated material was measured and evaluated for the oxygen permeability and the water vapor permeability. (4). Evaluation of retort suitability In the same manner as described above, a laminated material was used, the heat-sealing resin layer surfaces thereof were opposed to each other, and the outer peripheral edge was heat-sealed to produce a packaging bag. The inside is filled with the contents from the opening, and then the opening is sealed to produce a package. The package is put into a retort pot, and
After retort treatment at 0 ° C. for 30 minutes,
The above oxygen permeability and water vapor permeability were measured and evaluated. Regarding the above measurement results, Table 1 below shows the measurement results of the oxygen permeability and water vapor permeability of the barrier film and the laminated material, Table 2 shows the measurement results of the boiling suitability evaluation, and Table 3
Shows the measurement of retort suitability evaluation.

[0036] In Table 1 above, the oxygen permeability is cc / m ² / da
The unit is y · 23 ° C. · 90% RH, and the water vapor permeability is the unit of g / m ² / day · 40 ° C. · 100% RH. (After lamination) indicates the oxygen permeability and the water vapor permeability of the laminated material.

[0037] In Table 2 above, the oxygen permeability is cc / m ² / da
The unit is y · 23 ° C. · 90% RH, and the water vapor permeability is the unit of g / m ² / day · 40 ° C. · 100% RH.

[0038] In Table 3 above, the oxygen permeability is cc / m ² / da
The unit is y · 23 ° C. · 90% RH, and the water vapor permeability is the unit of g / m ² / day · 40 ° C. · 100% RH.

(1). As is clear from the results shown in Tables 1 to 3 above, those of Examples 1 to 5 had comparative oxygen permeability and water vapor permeability before boiling and before retorting. It was as good as, or better than, (2). Next, in the case of Examples 1 to 5, the oxygen permeability and the water vapor permeability after boiling and after retorting were all far greater than those of Comparative Examples 1 and 2. It was excellent.

[0040]

As apparent from the above description, according to the present invention, a coating film made of a resin composition containing a specific resin as a main component of a vehicle is excellent in tight adhesion to a polyamide resin film, and Focusing on the fact that the coating film functions as a water barrier film, first, on one surface of the polyamide-based resin film, a polyester-based resin, an acrylic-based resin, a hydrocarbon-based resin, or one of silicon-based resins or Forming a coating film of a resin composition containing two or more specific resins as a main component of a vehicle, and further depositing an inorganic oxide such as silicon oxide or aluminum oxide on the other surface of the polyamide resin film; Producing a barrier film by providing a thin film,
Further, at least a heat-sealing resin layer is provided on the vapor-deposited thin film surface of the inorganic oxide of the barrier film to produce a laminated material, and then the laminated material is used to form a bag. A packaging bag is manufactured. Thereafter, the contents are filled and packed in the packaging bag, and the opening is heat-sealed to produce a package, and the package is boiled or retorted. Subjected to heat sterilization treatment or heat cooking treatment to produce a packaged product, a coating film of a resin composition containing a specific resin as a main component of a vehicle has excellent close-adhesion with a polyamide resin film, and Prevents hot water and the like from entering the polyamide resin film during boiling or retort treatment, functions as a water barrier film, suppresses water absorption, swelling, shrinkage, and the like of the polyamide resin film, and further reduces the polyamide resin film. of Excellent adhesion between the surface and the deposited thin film of inorganic oxide. As a result, it has an extremely high barrier property against oxygen gas or water vapor, and has excellent transparency, fragrance retention, etc., and furthermore, a laminate strength. Also excellent, for example,
A barrier film useful for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, etc. in a boil or retort, and a laminate using the same 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 barrier film according to the present invention.

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

FIG. 3 is a schematic cross-sectional view showing a layer configuration of an example of a barrier film according to the present invention.

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

FIG. 5 is a schematic cross-sectional view showing a layer configuration of an example of a laminate using a barrier film according to the present invention.

FIG. 6 is a schematic configuration diagram of a plasma chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an inorganic oxide by a chemical vapor deposition method.

FIG. 7 is a schematic configuration diagram of a take-up type vacuum evaporation apparatus showing an outline of a method for forming a deposited thin film of an inorganic oxide by a physical vapor deposition method.

[Explanation of symbols]

A Barrier Film A ₁ Barrier Film A ₂ Barrier Film A ₃ Barrier Film S Laminate 1 Polyamide Resin Film 2 Coating Film 2a Water Barrier Film 3 Inorganic Oxide Thin Film 3a Inorganic Oxide Thin Film 3b Inorganic Oxide deposited thin film 4 Multilayer film 5 Printed picture layer 6 Heat-sealing resin layer

Continued on the front page F-term (reference) 3E086 BA04 BA13 BA15 BA24 BA33 BB51 BB71 CA01 CA11 CA28 CA29 CA35 DA08 4F006 AA38 AB24 AB35 AB39 AB74 BA05 CA07 DA01 4F100 AA17C AA17D AA19C AA19D AA20C AA20B AK02A00 AK02A00 AAKABAA BA07 BA10A BA10C BA10E EH66C EH66D EJ37B GB15 GB23 GB66 JC00 JD01 JD03 JD04 JD05A JK06 JL12E JN01

Claims (14)

[Claims] 1. A water barrier film comprising a coating film of a resin composition containing a resin as a main component of a vehicle is provided on one surface of a polyamide resin film, and a vapor-deposited thin film of an inorganic oxide is provided on the other surface. A barrier film provided. 2. The barrier film according to claim 1, wherein the polyamide resin film comprises a biaxially stretched nylon film. 3. The water barrier film is made of one of a polyester resin, an acrylic resin, a hydrocarbon resin, and a silicon resin.
2. The coating film according to claim 1, wherein the coating film is made of a resin composition containing at least one kind of a vehicle as a main component of the vehicle.
3. The barrier film described in any one of items 1 to 2. 4. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film is a single layer of an inorganic oxide vapor-deposited thin film formed by a chemical vapor deposition method or a multilayer film of two or more layers.
3. The barrier film according to 3. 5. The barrier film according to claim 4, wherein the inorganic oxide deposited thin film is a silicon oxide deposited thin film formed by plasma enhanced chemical vapor deposition. 6. The vapor-deposited thin film of an inorganic oxide, wherein the vapor-deposited thin film of silicon oxide is formed by plasma-enhanced chemical vapor deposition using an organosilicon compound as a monomer gas for vapor deposition. 6. The barrier film according to any one of items 1 to 5. 7. The method according to claim 7, wherein the inorganic oxide deposited thin film is made of silicon (Si).
And oxygen (O) as essential constituent elements, and further comprises one of carbon (C) and hydrogen (H), or a deposited thin film of silicon oxide containing both elements as trace constituent elements, The film thickness is in the range of 50 ° to 500 °, and the composition ratio of the essential constituent elements and the trace constituent elements is continuously changed in the film thickness direction. Item 7. A barrier film according to any one of Items 4 to 6. 8. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film comprises one or two or more multilayer films of the inorganic oxide vapor-deposited thin film formed by physical vapor deposition.
3. The barrier film according to 3. 9. The barrier film according to claim 8, wherein the inorganic oxide vapor-deposited thin film is a vapor-deposited inorganic oxide vapor-deposited thin film. 10. The barrier film according to claim 8, wherein the inorganic oxide vapor-deposited thin film comprises a vacuum-deposited aluminum oxide vapor-deposited thin film. 11. The method according to claim 1, wherein the deposited inorganic oxide thin film comprises a multilayer film of two or more layers of a deposited inorganic oxide thin film formed by a chemical vapor deposition method or a physical vapor deposition method. 4. The barrier film according to any one of items 1 to 3. 12. A vapor-deposited thin film of an inorganic oxide, wherein a vapor-deposited thin film of an inorganic oxide is provided by a chemical vapor deposition method, and then the inorganic oxide is deposited on the vapor-deposited thin film of the inorganic oxide by a physical vapor deposition method. The barrier film according to claim 11, comprising a multilayer film of two or more layers provided with a deposited thin film of an object. 13. A water barrier film comprising a coating film of a resin composition containing a resin as a main component of a vehicle is provided on one surface of a polyamide resin film, and a vapor-deposited thin film of an inorganic oxide is provided on the other surface. A laminate comprising at least a heat-sealing resin layer provided on the deposited inorganic oxide thin film of the barrier film. 14. A water barrier film comprising a coating film of a resin composition containing a resin as a main component of a vehicle is provided on one surface of a polyamide resin film, and a vapor-deposited thin film of an inorganic oxide is provided on the other surface. A laminated material for boiled or retorted treatment, wherein at least a heat-sealing resin layer is provided on the deposited inorganic oxide thin film of the provided barrier film.