JP2000117878A - Barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film excellent in the close adhesiveness with a vapor deposition film of inorg. oxide, enhanced in gas barrier properties to oxygen gas and steam and excellent in transparency, heat resistance, flexibility or laminate strength and a laminated material using the same. SOLUTION: A barrier film is characterized by that a vapor deposition membrane 3 of inorg. oxide due to a chemical gas phase growing method is provided on one surface of a base material film 2 and a coating film 4 comprising a resin compsn. containing an ethylene/vinyl alcohol copolymer as a main component of a vehicle and also containing at least one kind of a polymer rich in the close adhesiveness with the vapor deposition membrane 3 of inorg. oxide is provided on the vapor deposition membrane 3 of inorg. oxide and a laminated material using this 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 improved adhesion to a vapor-deposited thin film of an inorganic oxide, and a barrier against oxygen gas and water vapor. The present invention relates to a barrier film having excellent transparency, heat resistance, flexibility, and laminate strength, and a laminate 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, chemicals, daily necessities, miscellaneous goods, and the like.
In order to prevent the contents from deteriorating or the like, the above-mentioned packaging material is strongly required to have mainly a barrier property against oxygen gas or water vapor gas, that is, a so-called gas barrier property. By the way, as a barrier material against oxygen gas or water vapor gas, for example, aluminum foil, or an aluminum-deposited resin film obtained by vacuum-depositing aluminum on a plastic film by a vacuum deposition method or the like, and a polyvinylidene chloride-based material Resin or a film of a copolymer resin of vinylidene chloride and another monomer or a resin film in which a polyvinylidene chloride resin is coated on the surface of a plastic film, or polyvinyl alcohol or ethylene-vinyl acetate copolymer A film made of coalesced silicide,
On one side of a base film such as a plastic film,
Using a physical vapor deposition method (PVD method) such as a vacuum evaporation method,
For example, using a vapor deposition film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, or a chemical vapor deposition method (CVD method) such as a low-temperature plasma chemical vapor deposition method,
For example, a deposition film provided with a deposition film of an inorganic oxide such as silicon oxide and aluminum oxide is known. These barrier materials are laminated with other plastic films or materials such as paper base materials, etc., for example, and filled and packed with various articles such as food and drink, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. To provide useful packaging materials.

[0003]

However, the above-mentioned barrier materials have oxygen gas barrier properties, water vapor gas barrier properties, etc., and can be expected to have a certain effect. The fact is that it is not satisfactory enough. For example, the above-mentioned aluminum foil is a gas barrier material having an excellent gas barrier property against oxygen gas, water vapor gas, and the like.
In addition to the problem of disposal after use, there is also the problem that the contents cannot be visually recognized from the outside in the packaged product filled with the contents because it is basically an opaque material. There is. Next, as for the aluminum-deposited resin film obtained by vacuum-depositing aluminum on the plastic film by a vacuum deposition method or the like, similarly to the aluminum foil described above, the contents are discarded after use, and the contents are visually recognized from the outside. Not only is there a problem that it cannot be obtained, but the gas barrier property is inferior to that of aluminum foil, so that it is not necessarily a satisfactory barrier material.

Further, regarding the above-mentioned polyvinylidene chloride-based resin, a film made of a copolymer resin of vinylidene chloride and another monomer or a plastic film coated with a polyvinylidene chloride-based resin on the surface thereof, It is widely used as a resin-based barrier material, but it is not preferable in terms of environmental protection because it generates chlorine-based gas in incineration treatment after use. In fact, it is not sufficient and cannot be used for filling and packaging contents that require a high level of barrier properties. Next, the film composed of the above-mentioned polyvinyl alcohol or a saponified ethylene-vinyl acetate copolymer shows relatively excellent oxygen gas barrier properties under absolute dry conditions, but has insufficient steam gas barrier properties. Also, under humidity conditions, the oxygen gas barrier properties also deteriorate significantly,
Under practical conditions, it cannot be said that the material is a sufficiently satisfactory barrier material. In order to improve the above-described humidity dependency, various methods and the like have been developed and proposed. For example, a method of depositing a deposited film of an inorganic oxide such as silicon oxide using a vacuum deposition method or the like. Has been proposed, but humidity 7
Under high humidity conditions of 0% or more, deterioration of oxygen gas barrier properties cannot be improved (Japanese Patent Laid-Open No. 4-713).
No. 9).

Next, on one surface of the above-mentioned base film such as a plastic film, an inorganic material such as silicon oxide, aluminum oxide or the like is formed by a physical vapor deposition method (PVD method) such as a vacuum evaporation method. In the case of a vapor-deposited film provided with an oxide vapor-deposited film, whether or not the gas barrier properties against oxygen gas, water vapor gas, and the like are significantly improved depends largely on the heat resistance of the base film. For example, when a heat-resistant base film such as a polyethylene terephthalate film is used as the base film, a vapor-deposited film can be favorably formed by a vacuum vapor-deposition method or the like, and the gas barrier property against oxygen gas and the like can be obtained. It is possible to achieve the effect of improving the like. However, when a base film having poor heat resistance such as a biaxially stretched polypropylene film, a non-stretched polypropylene film, or a low-density polyethylene film is used, it is technically necessary to form a vapor-deposited film by a vacuum vapor deposition method or the like. Although it is possible, it is difficult to improve the gas barrier property against oxygen gas and the like, so that it cannot always be said to be sufficiently satisfactory. Further, as the above-mentioned base film, for example, when a polyethylene terephthalate film is used, the polyethylene terephthalate film has rigidity, is hard, and is liable to generate wrinkles or the like on the film. However, there is a problem that it is not suitable for packaging materials requiring flexibility and the like.

Further, a chemical vapor deposition (CVD) method such as a low-temperature plasma-enhanced chemical vapor deposition (CVD) method is applied to one surface of the base film such as the plastic film to form, for example, silicon oxide or aluminum oxide. With respect to a vapor-deposited film provided with a vapor-deposited film of an inorganic oxide, it is said that, during the formation of the vapor-deposited film, the thermal damage to the base film is small, and the vapor-deposited film of the inorganic oxide can be formed on various plastic films. It has advantages and has attracted much attention in recent years. For example, there has been proposed a method of forming a silicon oxide vapor-deposited film on a polyolefin resin molded article having poor heat resistance by using a plasma chemical vapor deposition method (see Japanese Patent Application Laid-Open No. 5-287103). However, in the above method, after laminating the sealant film, the oxygen gas barrier property is 5 cc / m ² or more, and it can be said that a sufficiently satisfactory oxygen gas barrier property can always be achieved. The fact is that there is no such thing. Further, in the above, in order to improve the oxygen gas barrier property, the thickness of the inorganic oxide vapor-deposited film must be formed to 1000 ° or more, and in such a case, the polyolefin having poor heat resistance. There is a problem that it is necessary to solve the problem of strength deterioration due to the plasma reaction of the base resin film. Further, when the thickness of the deposited film of the inorganic oxide is increased, the deposited film itself exhibits a yellow tint, and when used as a packaging material for filling and packaging foods and drinks, there is a problem that the commercial product is affected. There are points.

Further, using a physical vapor deposition method (PVD method) such as the above-described vacuum deposition method, for example, a deposition film provided with a deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, or a low-temperature deposition film. For example, in a vapor-deposited film provided with a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide using a chemical vapor deposition method (CVD method) such as a plasma-enhanced chemical vapor deposition method, after forming the vapor-deposited film, Further, a barrier resin such as an ethylene-vinyl alcohol copolymer is used on the deposited film, and a coating film or a laminated film of the barrier resin is provided to form a two-layer barrier film. However, it has also been proposed to further improve the gas barrier property, but the tight adhesion between the deposited film of the inorganic oxide and the coating film or the laminated film formed of the barrier resin is poor, and the laminating suitability is poor. Phenomenon occurs such as Rami, and it is capable of sufficiently satisfactory is the actual situation that not say. Therefore, the present invention improves the tight adhesion between the inorganic oxide and the vapor-deposited film, and has excellent gas barrier properties against oxygen gas and water vapor gas, and furthermore, transparency, heat resistance, flexibility and laminating properties.
An object of the present invention is to provide a barrier film excellent in suitability and a laminated material using the same.

[0008]

As a result of various studies to solve the above problems, the present inventor has found that a thin film of inorganic oxide deposited by chemical vapor deposition and a thin film of inorganic oxide deposited thereon. Focusing on a polymer rich in close adhesion with, first, on one side of the substrate film, provided a vapor-deposited thin film of inorganic oxide by chemical vapor deposition, and further, A resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle and at least one or more of a polymer having high adhesion to a vapor-deposited thin film of the above-mentioned inorganic oxide. A barrier film is manufactured by providing a coating film made of a material, and another plastic film or a paper base material or other material is arbitrarily laminated on the barrier film to form a laminated material. Manufacturing,
Next, using the laminated material, it is made into a bag or a box to produce a packaging container. In the packaging container, for example, food and drink, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. When packed products are manufactured by filling and packaging various products, they have excellent adhesion to inorganic oxide vapor-deposited thin films, improve their gas barrier properties against oxygen gas, water vapor, etc., and alter or modify the contents. It has a stable long-term distribution, storage suitability, etc., by preventing etc., and since it is excellent in transparency, the contents can be visually recognized from the outside, and further, flexibility, heat resistance, Completed the present invention by finding a useful barrier film which is excellent in laminate strength and the like, has no breakage, etc., and can produce extremely excellent and good packaging products at low cost, and a laminated material using the same. It is.

That is, according to the present invention, a vapor-deposited thin film of an inorganic oxide is provided on one surface of a substrate film by a chemical vapor deposition method, and an ethylene-vinyl alcohol is further deposited on the vapor-deposited thin film of an inorganic oxide. As the main component of the vehicle,
And a barrier film provided with a coating film of at least a resin composition containing one or more polymers having high adhesion to the above-mentioned vapor-deposited thin film of inorganic oxide. It relates to a laminated material using the same.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to the drawings. The layer structure of the barrier film according to the present invention and the laminated material using the same will be described more specifically with reference to the drawings.
FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of a barrier film according to the present invention, and FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of a laminate according to the present invention.

First, the barrier film 1 according to the present invention
As shown in FIG. 1, on one surface of the base film 2,
Providing a vapor-deposited thin film 3 of inorganic oxide by chemical vapor deposition,
Further, an ethylene-vinyl alcohol copolymer is used as a main component of the vehicle on the inorganic oxide vapor-deposited thin film 3, and has a good adhesion to at least the inorganic oxide vapor-deposited thin film 3. The basic structure is such that a coating film 4 made of a resin composition containing one or more polymers is provided. Next, as shown in FIG. 2, the laminated material 1a according to the present invention is provided on the surface of the coating film 4 constituting the barrier film 1 shown in FIG. And a basic structure comprising at least a heat-sealing resin layer 6 on the entire surface including the printed picture layer 5. In FIG. 2, 2, 3 and the like in the drawing have the same meaning as described above. The above exemplification is an example of the barrier film and the laminate according to the present invention, and the present invention is not limited thereto. For example, although not shown, in the above laminated material,
Depending on the contents to be filled and packed, the purpose of use, and the like, other plastic films, paper substrates, etc. can be arbitrarily laminated at desired positions to produce a laminated material.

Next, in the present invention, the barrier film according to the present invention and the material, material, manufacturing method and the like constituting the laminated material will be described. First, the barrier film according to the present invention or the laminated material Examples of the base film include: polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyamide resins; polycarbonate resins; and polystyrene. Resin, polyvinyl alcohol, ethylene-
Polyvinyl alcohol such as saponified part of vinyl acetate copolymer
Uses films or sheets of various resins such as vinyl resin, polyacrylonitrile resin, polyvinyl chloride resin, polyvinyl acetal resin, polyvinyl butyral resin, fluorine resin, etc. can do. Thus, in the present invention, the above resin film or sheet is used.
For example, a method in which one or more of the above resins are used and the above resins are formed alone by using a film forming method such as an inflation method, a T-die method, or the like. Alternatively, a method of forming a multilayer co-extrusion film using two or more different resins, or a method of mixing and forming a film before forming a film using two or more resins. , A resin film or sheet is produced, and further stretched in a uniaxial or biaxial direction by using, for example, a tenter method or a tuber method. Can be used. In the present invention, the thickness of the base film is about 5 to 200 μm,
More preferably, about 10 to 50 μm is desirable. In addition,
In the above, at the time of film formation of the resin, for example, the workability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, mold resistance, Various plastic compounding agents and additives can be added for the purpose of improving and modifying the electric characteristics and others, and the amount of addition can be from a very small amount to several tens% depending on the purpose. And can be arbitrarily added. 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, Fungicides,
Pigments, others, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the base film is
If necessary, for example, corona discharge treatment, ozone treatment,
Pretreatment such as low-temperature plasma treatment using oxygen gas, nitrogen gas, or the like, glow discharge treatment, oxidation treatment using chemicals, or the like, and the like can be arbitrarily performed. The surface pre-treatment may be performed in a separate step before forming a vapor-deposited thin film of an inorganic oxide.For example, in the case of a surface treatment such as a low-temperature plasma treatment or a glow discharge treatment, As a pretreatment for forming a vapor-deposited thin film of oxide, pretreatment can be performed by in-line treatment. In such a case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is carried out as a method for improving the adhesion between the base film and the deposited thin film of the inorganic oxide. On the surface of the material film, a primer coat agent layer, an undercoat agent layer, a vapor-deposited anchor coat agent layer, or the like can be arbitrarily formed in advance. 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. The coating can be performed by using a coating method such as a coating method, a kiss coating method, or the like. It can be carried out by in-line processing or the like of axial stretching processing. In the present invention, as the substrate film, specifically, a biaxially stretched polypropylene film,
It is desirable to use a biaxially oriented polyethylene terephthalate film or a biaxially oriented nylon film.

Next, in the present invention, the vapor-deposited thin film of the inorganic oxide formed by the chemical vapor deposition method constituting the barrier film or the laminated material according to the present invention will be described. Examples of the deposited thin film of a substance include chemical vapor deposition (Ch) such as plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.
electrical Vapor Deposition method,
A vapor-deposited thin film of an inorganic oxide can be formed using, for example, a CVD method. In the present invention, specifically, on one surface of the base 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. Further, an oxygen gas or the like is used as an oxygen supply gas, and a plasma-enhanced chemical vapor deposition (CVD) method using a low-temperature plasma generator or the like.
Method) to form a deposited thin film of an inorganic oxide such as silicon oxide. In the above description, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, 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-described 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. 3 described above, in the present invention, the vacuum chamber-1 of the plasma enhanced chemical vapor deposition apparatus 11 is used.
The base film 2 is fed out from an unwinding roll 13 disposed in the inside 2, and the base film 2 is further cooled at a predetermined speed on the peripheral surface of the electrode drum 15 via an auxiliary roll 14. Transport. 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,
Then, a plasma is generated by the glow discharge plasma 20 on the base film 2 conveyed on the peripheral surface of the cooling / electrode drum 15 and is irradiated with the plasma to generate inorganic plasma such as silicon oxide. A vapor-deposited thin film is formed and a film is formed. In the present invention, the cooling / electrode drum 1
5 is provided with a predetermined power from a power source 21 disposed outside the chamber.
The generation of plasma is promoted by disposing a magnet 22 in the vicinity of the substrate film 2. Next, the base film 2 on which the deposited thin film of the inorganic oxide such as silicon oxide is formed,
It can be wound on a take-up roll 24 via a roll 23 to produce a deposited thin film of inorganic oxide by the plasma enhanced chemical vapor deposition method according to the present invention. In the figure, reference numeral 25 denotes 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 vapor-deposited thin film of silicon oxide formed above reacts chemically with a monomer gas such as an organic silicon compound and oxygen gas, and the reaction product adheres tightly to the substrate film. dense, it is possible to form a thin film rich in flexibility, usually, the general formula SiO _X (provided that, X is 0
(Representing the number of 2 to 2). Thus, from the viewpoints of transparency, barrier properties, etc., the silicon oxide deposited thin film has the general formula Si
O _X (provided that, X represents represents. A number of 1.3 to 1.9) is intended is preferably a thin film mainly composed of vapor-deposited film of silicon oxide represented by. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, and the like. In general, as the value of X decreases, the gas permeability decreases, but the value of the film itself increases. It has a yellow color and poor transparency. Further, the above-described deposited silicon oxide thin film has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or
It consists of a deposited film of silicon oxide containing both elements as trace constituent elements, and has a thickness of 50 ° to 500 °.
And the composition ratio between the essential constituent elements and the trace constituent elements continuously changes in the film thickness direction. Further, the above-mentioned silicon oxide deposited thin film is
When a compound comprising carbon is contained, the carbon content is reduced in the depth direction of the film thickness. Thus, in the present invention, the above-mentioned deposited thin film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Spec).
Troscopy, XPS), secondary ion mass spectrometer (Secondary Ion Mass Spect)
roscopy, SIMS), etc.
The physical properties as described above can be confirmed by performing elemental analysis of the deposited thin film of silicon oxide using a method of performing analysis by ion etching in the depth direction or the like. Further, in the present invention, the thickness of the above-mentioned evaporated silicon oxide thin film is desirably about 1000 ° or less, and specifically, the thickness is about 50 to 500.
Å position, more preferably, 100-300 ° position, and thus, in the above, 300 °, and more preferably 500 °
If it is thicker, cracks and the like are likely to occur in the film, which is not preferable.
If it is less than this, it is difficult to achieve the effect of the barrier property, which is not preferable. In the above description, the film thickness can be measured, for example, by a fundamental parameter method using a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited silicon oxide thin film, increasing the volume velocity of the deposited film,
That is, it can be performed by a method of increasing the amounts of the monomer gas and the oxygen gas, a method of reducing the deposition rate, or the like. In the case where a thin film of an inorganic oxide is formed by a plasma enhanced chemical vapor deposition method on a substrate film having poor heat resistance, such as the above-described substrate film, when the deposition rate is reduced, the substrate is exposed to plasma. It is not preferable because the time becomes longer and the base film or the like deteriorates.
It is preferable to form a deposited film at a deposition rate of 200 n / min.

Next, in the present invention, the bag according to the present invention is described.
Ethylene for rear film or laminated material
-A vinyl alcohol copolymer as the main component of the vehicle,
Close adhesion with this, at least with the deposited thin film of inorganic oxide
COMPOSITION CONTAINING ONE OR MORE VARIOUS POLYMERS
The coating film made of a material will be described.
-For example, ethylene-vinyl alcohol
One or more of the call copolymers may comprise a main component of the vehicle.
Minutes, and at least, a deposited thin film of inorganic oxide
Add one or more polymers with high adhesion
And, if necessary, for example, fillers, stabilizers, plastics
Agents, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants,
Thickener, desiccant, lubricant, antistatic agent, crosslinking agent, etc.
Add the optional additives described above and knead thoroughly with a solvent, diluent, etc.
Solvent type, aqueous type, emulsion type, etc.
A resin composition consisting of:
Used, for example, roll coating method, gravure roll coating
Method, kiss roll coating method, squeeze roll coating
Method, reverse roll coating method, curtain coating
Coating method by coating method
Amount, for example, 0.1 g / m ^Two-10 g / m^Two(Dry
State), preferably 0.5 g / m^Two~ 5g / m^Two(Dry
(Dry state) and then heating
After drying and further aging treatment, the present invention
Such a coating film can be formed. Above
The above resin composition includes ethylene-vinyl alcohol.
Close adhesion to the deposited thin film of the alcohol copolymer and inorganic oxide
Dissolve or knead the polymer rich in
Since it is hardened, use an alcohol-water solution or the like.
It is preferable to use a resin composition adjusted in
As the alcohol component, for example, n-pro
Pill alcohol, isopropyl alcohol, n-butano
-T-butanol, ethyl alcohol, methyl alcohol
Calls and the like can be used.
In a water-based solution, the mixing ratio of alcohol and water
For example, for alcohol, 50 to 70 parts by weight
Water, 50 to 30 parts by weight of alcohol water
It is desirable to adjust the system solution.

In the above, ethylene-vinyl alcohol
Examples of the ethylene-vinyl acetate copolymer include ethylene-vinyl acetate copolymer having an ethylene content of 25 to 50 mol%, which is obtained by completely saponifying an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 79 to 92 wt%. Coalescing can be used. The ethylene-vinyl alcohol copolymer has a high gas barrier property, and is further excellent in fragrance retention, transparency, and the like. % Or less is not preferred because the oxygen gas barrier property is rapidly lowered and the transparency is deteriorated, and if less than 25 mol%, the thin film becomes brittle and It is not preferable because the gas barrier property is lowered.

Next, in the above, as the polymer having a good adhesion to the deposited thin film of the inorganic oxide, for example,
One or more of a polyethyleneimine-based polymer, a polycarbodiimide-based polymer, and a polyvinylpyrrolidone-based polymer can be used. Specifically, examples of the polyethyleneimine-based polymer include N-unsubstituted polyalkyleneimines such as polyethyleneimine, N-alkyl-substituted polyalkyleneimines, and N-alkylsubstituted polyalkyleneimines.
-Acyl-substituted polyalkyleneimine and the like can be used, and as the above-mentioned polycarbodiimide-based polymer, for example, polycarbodiimide and the like can be used, and further, as the above-mentioned polyvinylpyrrolidone-based polymer, For example, polyvinylpyrrolidone, polyalkylated vinylpyrrolidone, a copolymer of vinylpyrrolidone and vinyl acetate, a copolymer of vinylpyrrolidone and styrene, and the like can be used. In the present invention, the reason why the above-mentioned polymer is rich in close adhesion to a vapor-deposited thin film of an inorganic oxide is not clear, but the carbodiimide group, imine group, pyrrolidone group and the like of the polymer are ethylene-vinyl alcohol-. The interaction between the ethylene-vinyl alcohol copolymer and the vapor-deposited thin film of inorganic oxide, etc. by causing an interaction such as a hydrogen bond with each of the hydroxyl groups in the copolymer or the vapor-deposited thin film of inorganic oxide. It is presumed to be due to the development of the improvement. In the resin composition according to the present invention, the mixing ratio of the ethylene-vinyl alcohol copolymer and the polymer having a high adhesion to the vapor-deposited thin film of the inorganic oxide is ethylene-vinyl alcohol-copolymer. 100 parts by weight of the copolymer, a polymer having a high adhesion to a deposited thin film of an inorganic oxide.
A blending ratio of 0 parts by weight is preferable.

Next, in the resin composition according to the present invention, a silane coupling agent having dual reactivity can be added as a crosslinking agent or the like. Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ
-Mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β -Hydroxyethyl) -γ-aminopropyltriethoxysilane, one or more of γ-aminopropylsilicone can be used.
As the amount of use, only a small amount may be added.

In the present invention, the above-mentioned ethylene-vinyl alcohol copolymer is used as a main component of the vehicle, and at least a polymer having a good adhesion to a vapor-deposited thin film of an inorganic oxide is added thereto. Further, if necessary, a silane coupling agent or the like is added, and if necessary, other additives are optionally added. The resin is sufficiently kneaded with an alcohol-water-based solvent, a diluent, or the like. A coating film can be formed by preparing a composition, coating the composition by a usual coating method, and then subjecting the composition to heat drying and further aging treatment. Thus, the above-mentioned coating film is excellent in close adhesion to a vapor-deposited thin film of an inorganic oxide, improves its barrier property against oxygen gas, water vapor gas, etc., and further has transparency, heat resistance and hot water resistance. , Laminating suitability, etc. In the present invention, although its mechanism and the like are not clear, an ethylene-vinyl alcohol copolymer is used as a main component of the vehicle. By adding a seed or more, the cured film of the ethylene-vinyl alcohol copolymer described above is mixed with a cured film of a polymer having high adhesion to the vapor-deposited thin film of the inorganic oxide, and The two interact with each other to form a coating film, thereby improving the tight adhesion between the coating film and the inorganic oxide vapor-deposited thin film. It is presumed that the two-layered barrier film with the thin film has the effect of further improving the barrier properties against oxygen gas or water vapor gas.
Further, in the present invention, in the resin composition according to the present invention, by adding a silane coupling agent or the like having the above-described dual reactivity, ethylene-vinyl alcohol-
A polymer or the like having a high adhesion to a vapor-deposited thin film of an inorganic oxide or an inorganic oxide forms a three-dimensionally networked coating film via the silane coupling agent or the like, and the inorganic oxide It is possible to improve the close adhesion of the substance to the deposited thin film and to further improve the barrier property against oxygen gas, water vapor and 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 an ink composition such as a relief printing ink composition, a screen ink composition, etc., 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. 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,
Optionally add additives such as stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc. It is possible to use ink compositions in various forms which are sufficiently kneaded with a diluent or the like.

Further, in the present invention, the heat-sealing resin forming the heat-sealing resin layer constituting the laminated material according to the present invention may be, for example, melted by heat and mutually melted. Any material can be used, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- Ethyl acrylate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene is used to prepare acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fuma- Resin consisting of one or more resins such as acid-modified polyolefin resins, polyvinyl acetate resins, polyester resins, polystyrene resins, etc., modified with unsaturated carboxylic acids such as luic acid, itaconic acid and others. Can be used. Thus, in the present invention, as the heat-sealing resin layer,
Using one or more of the above resins, for example, a resin film or sheet formed into a film by a method such as an inflation method, a T-die method, or the like; It can be used as a coating film made of a resin composition containing one or more resins as a main component of the vehicle. As the film thickness,
About 5 to 100 μm, preferably about 10 to 50 μm is desirable.

In the present invention, among the above resins, it is particularly preferable to use a linear (linear) low-density polyethylene. The above-mentioned linear low-density polyethylene has the advantage of having a small amount of propagation of rupture due to its tackiness and improving impact resistance. It is also effective for preventing deterioration of environmental stress cracking properties. In the present invention,
Other resins can be blended with the linear low-density polyethylene. For example, by blending an ethylene-butene copolymer or the like, the heat stability is slightly lowered and the seal stability is deteriorated in a high temperature environment. Although there is a tendency, there is an advantage that the tearing property is improved and contributes to easy opening. Further, in the present invention, as the linear low-density polyethylene as the heat-sealing resin, specifically, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is used. be able to. To be more specific, Mitsubishi Chemical Corporation's product name "Kernel", Mitsui Petrochemical Industry Co., Ltd. product name "Evolu", USA,
EXXON CHEMICAL
Using a metallocene catalyst such as "EXACT" (trade name, manufactured by Dow Chemical Co., Ltd.), "Affinity" (trade name), manufactured by DOW CHEMICAL, USA, and "ENGAGE" (trade name) A polymerized ethylene-α-olefin copolymer can be used. In the present invention, when an ethylene-α-olefin copolymer polymerized using the above metallocene catalyst is used, a low-temperature
This has the advantage that sealability is possible.

Further, in the laminated material according to the present invention,
Normally, packaging containers are subjected to severe physical and chemical conditions, so that the laminated material constituting the packaging container is required to have strict packaging suitability, deformation prevention strength, drop impact strength, Various conditions such as pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. Therefore, the present invention satisfies the above conditions. Materials can be selected and used arbitrarily, and in addition to the above-mentioned materials constituting the laminated material according to the present invention, any desired material can be further 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 Bromide based resin, polycarbonate - Bonnet - DOO resins, polyvinyl alcohol - Le resins, ethylene - saponified vinyl acetate copolymer, fluorine resin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. 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 3 μm.
It can be used by selecting from a range of about 00 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.

Next, in the present invention, the barrier film, printed picture layer, heat-sealing resin layer,
Further, as a method of manufacturing the laminated material according to the present invention using other materials and the like, for example, a dry lamination method of laminating via a laminating adhesive layer with a laminating adhesive, Alternatively, it can be performed by an extrusion lamination method or the like in which a melt-extruded adhesive resin is laminated via a melt-extruded resin layer. In the above,
Examples of the laminating adhesive include one-component or two-component curable or non-curable vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, and epoxy. Adhesives for laminating such as solvent type, aqueous type, emulsion type and the like can be used. Examples of the coating method of the adhesive for laminating include direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating and the like. Method, Fonten method, transfer roll coating method, etc., and the coating amount is 0.1 to 10 g / m ² (dry state).
And more preferably about 1 to 5 g / m ² (dry state). In the present invention, for example, an adhesion promoter such as a silane coupling agent can be optionally added to the adhesive for laminating. Next, in the above, as the melt-extruded adhesive resin, the above-mentioned heat-sealing resin forming the heat-sealing resin layer can be used in the same manner. Thus, in the present invention,
As the melt-extruded adhesive resin, it is particularly preferable to use low-density polyethylene, particularly, linear low-density polyethylene and acid-modified polyethylene. The thickness of the melt-extruded resin layer of the melt-extruded adhesive resin is about 5 to 100 μm, more preferably about 10 to 100 μm.
About 50 μm is desirable. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the above-mentioned lamination, if necessary, for example, an adhesive improving agent such as an anchor coat agent may be coated. You can also. Specific examples of the above-mentioned anchor coating agent include organic titanium-based anchor coating agents such as alkyl titanate, isocyanate-based anchor coating agents, and polyethyleneimine-based anchor coating agents. Various aqueous or oil-based anchor coating agents, such as a coating agent, a polybutadiene-based anchor coating agent, and the like, can be used. Thus, in the present invention,
The above-mentioned anchor coating agent is coated by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and a solvent and dilution. By drying the agent or the like, an anchor coat agent layer 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).

The oxygen permeability of the laminated material according to the present invention produced as described above is a temperature of 23 ° C. and a relative humidity of 90% R
In H, the effect is 0.5 cc / m ² · day · atm or less. The above-described measurement of the oxygen permeability is carried out by the aforementioned method, for example, MOCON (MOCO, USA).
23 ° C., 90% using an oxygen permeability measuring instrument (model name, OX-TRAN 2/20) manufactured by N)
It can be measured under RH conditions.

The laminated material according to the present invention produced as described above can be used for packaging in various useful forms suitable for filling and packaging various articles by making it into a bag or a box. A container can be manufactured. That is,
In the present invention, packaging containers of various forms are manufactured by bag-making or box-making using the laminated material according to the present invention. It has excellent gas barrier properties, transparency, heat resistance, impact resistance, etc., and also has post-processing suitability such as laminating, printing, bag making or box making. It has excellent suitability for packing and preserving various chemicals and cosmetics such as detergents, shampoos, oils, toothpastes, adhesives and pressure-sensitive adhesives, and various other articles. In the above, the method of bag making or box making will be described.For example, in the case of a soft packaging bag, the laminated material produced above is used, and the surface of the heat-sealing resin layer of the inner layer is made to face, The bag can be formed by folding the sheet or stacking the two sheets, and further heat sealing the peripheral end to provide a seal portion. That is, as the bag making method, the above-mentioned laminated material is folded with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further formed, for example, by a side seal type. , 2 way seal type, 3 way seal type, 4 way seal type, envelope pasting seal
Seals, gasoline-sealed seals (pyro-seals), pleated seals, flat-bottomed seals, square-bottomed seals, etc.
Various types of packaging containers according to the present invention can be manufactured by heat-sealing in the form of a seal. In addition, for example, a self-standing packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the above-described laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal,
Can be performed by a known method such as 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 container manufactured as described above, for example,
It is used for filling and packaging of various articles such as various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, sundries, and others.

[0031]

The present invention will be described more specifically with reference to the following examples. Example 1 (1). As a base material, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, which was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a deposited silicon oxide thin film having a thickness of 120 ° was obtained under the following conditions. Was formed on one surface of the above biaxially stretched polyethylene terephthalate film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2). Next, a silicon oxide deposited thin film was formed as described above.
Use of axially stretched polyethylene terephthalate film,
Using a gravure printing machine, a gravure coat roll is placed on the first color of the silicon oxide deposited thin film surface,
100 parts by weight of a 15% solution of an ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent was added to polyethyleneimine (Nippon Shokubai Kagaku). A resin composition prepared by adding 20 parts by weight of a 5% solution (produced by Co., Ltd.) is coated by a gravure roll coating method to have a thickness of 1.1 g / m ² (dry state). To form a coating film, and then heat-treated at 120 ° C. for 5 minutes.
A barrier film according to the present invention was manufactured by forming a cured film. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. (3). Next, the biaxially stretched polyethylene terephthalate film on which the printed picture layer was formed was dry-laminated.
Is mounted on the first delivery roll of the printing machine, and a two-part curable polyurethane-based laminating adhesive of 4.5 g / m ² (dry) is applied to the printed pattern layer surface by a gravure roll coating method. (Weight) to form an adhesive layer for laminating. Next, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material according to the present invention.

Embodiment 2 (1). As a substrate, a biaxially stretched polypropylene film having a thickness of 20 μm (trade name, G, manufactured by Nimura Chemical Industry Co., Ltd.)
HI, one-sided corona-treated product), which was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Formed on one side of the film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 70 m / min Evaporation surface: Corona treated surface (2). Next, a silicon oxide deposited thin film was formed as described above.
Using a gravure printing machine, a gravure coat roll was placed on the first color of the silicon oxide vapor-deposited thin film surface of the axially stretched polypropylene film, and an ethylene-vinyl alcohol copolymer (ethylene content 32%) was used. Mol%) of ion-exchanged water and n-propyl alcohol (1/1) solvent at 15%
Using a resin composition obtained by adding 5 parts by weight of a 15% solution of polycarbodiimide (manufactured by Nisshinbo Co., Ltd.) to 100 parts by weight of the solution, and coating it by a gravure roll coating method, A coating film having a thickness of 1.1 g / m ² (dry state) was formed, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. Manufactured. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. (3). Next, the biaxially stretched polypropylene film having the printed pattern layer formed thereon is mounted on a first delivery roll of a dry laminating machine, and a two-component curing type is formed on the printed pattern layer surface using a gravure roll coating method. Was applied at a rate of 4.5 g / m ² (dry weight) to form an adhesive layer for laminating. 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 3 (1). A 15-μm-thick biaxially stretched nylon film was used as a base material, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a deposited silicon oxide thin film having a thickness of 150 ° was formed under the following conditions. It was formed on one side of a biaxially stretched nylon film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 70 m / min Evaporation surface: Corona treated surface (2). Next, a silicon oxide deposited thin film was formed as described above.
Using a gravure printing machine, a roll for gravure coating was placed on the first color of the silicon oxide vapor-deposited thin film of the axially stretched nylon film, and an ethylene-vinyl alcohol copolymer (ethylene content 29 Mol%) ion-exchanged water and n-
A resin composition obtained by adding 5 parts by weight of a 10% solution of polyvinylpyrrolidone to 100 parts by weight of a 15% solution in a propyl alcohol (1/1) solvent is used, and this is subjected to a gravure roll coating method. And the thickness is 1.
A coating film of 1 g / m ² (dry state) was formed, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film, thereby producing a barrier film according to the present invention. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. (3). 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. Next, a 70 μm-thick stretched polypropylene film was dry-laminated on the above-mentioned adhesive layer surface for a laminate, to produce a laminate according to the present invention.

Example 4 In (3) of Example 1 described above, the thickness of the biaxially stretched polyethylene terephthalate film on which the print pattern layer was formed was placed on the surface of the print pattern layer via a laminating adhesive layer. 70
Instead of dry laminating a low-density polyethylene film of μm to produce a laminate, a biaxially stretched polyethylene terephthalate film having a printed picture layer formed thereon is extruded and mounted on a first delivery roll of a laminating machine. Using a low-density polyethylene for melt extrusion on the surface of the printed pattern layer, while extruding this to a thickness of 20 μm,
A 70 μm-thick low-density polyethylene film was extruded and laminated, and the other conditions were the same as in Example 1 to produce a laminate according to the present invention.

Example 5 In (3) of Example 2 described above, the biaxially stretched polypropylene film on which the print pattern layer was formed,
Instead of dry laminating a 70 μm-thick unstretched polypropylene film through a laminating adhesive layer to produce a laminate, a biaxially stretched polypropylene film having a printed picture layer formed thereon is extruded by a laminating machine. , And using a low-density polyethylene for melt extrusion on the surface of the printed pattern layer, while extruding this to a thickness of 20 μm, extruding a 70 μm thick unstretched polypropylene film. The laminated material according to the present invention was manufactured in the same manner as in Example 2 except that the laminate was laminated.

Example 6 In Example 3 (3) above, a 70 μm-thick non-coated nylon film having a 70 μm thickness was placed on the printed pattern layer surface of a biaxially stretched nylon film having a printed pattern layer formed thereon via a laminating adhesive layer. Instead of dry laminating the stretched polypropylene 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. Using a low-density polyethylene for melt extrusion on the surface, a 70 μm-thick unstretched polypropylene film was extruded and laminated while being melt-extruded to a thickness of 20 μm. Similarly, a laminated material according to the present invention was produced.

Comparative Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a substrate, and one surface of the biaxially stretched polyethylene terephthalate film was used in the same manner as in Example 1 above. Then, a thin film of silicon oxide is formed on the thin film of silicon oxide, and then a gravure coat roll is placed on the first color of the silicon oxide film using a gravure printing machine. A resin composition consisting of 100 parts by weight of a 15% solution of styrene-copolymer (ethylene content 32 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent is used. -Luco-
Coating by a coating method to form a coating film having a thickness of 1.1 g / m ² (dry state).
The coating was cured by heating for 1 minute to produce a barrier film. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. Further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, a low-density polyethylene film having a thickness of 70 μm is prepared, one surface of which is subjected to corona discharge treatment, and the surface of the adhesive layer for laminating the biaxially stretched polyethylene terephthalate film on the corona discharge treated surface. Were opposed to each other, and both were laminated by a dry lamination method to produce a laminated material.

Comparative Example 2 A biaxially oriented polypropylene film having a thickness of 20 μm was used as a substrate, and silicon oxide was deposited on one surface of the biaxially oriented polypropylene film in exactly the same manner as in Example 2 above. A thin film is formed, and then a gravure coating roll is arranged on the first color of the silicon oxide vapor-deposited thin film using a gravure printing machine, and an ethylene-vinyl alcohol copolymer is placed. A resin composition consisting of 100 parts by weight of a 15% solution of ion-exchanged water (ethylene content 32 mol%) and n-propyl alcohol (1/1) solvent was used, and this was subjected to a gravure roll coating method. To form a coating film having a thickness of 1.1 g / m ² (dry state), followed by a heat treatment at 120 ° C. for 5 minutes.
A hardened film was formed to produce a barrier film. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. Further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, a non-stretched polypropylene film having a thickness of 70 μm is prepared, one surface of which is subjected to a corona discharge treatment, and the laminating adhesive layer surface of the biaxially stretched polypropylene film is opposed to the corona discharge treated surface. And both were laminated by a dry lamination method to produce a laminated material.

Comparative Example 3 As a base material, a biaxially stretched nylon film having a thickness of 15 μm
And the biaxial extension was performed in exactly the same manner as in Example 3 above.
On one side of the drawn nylon film, a thin film of silicon oxide is deposited.
Is formed on the surface of the silicon oxide film.
Use a via printing machine for the gravure coating on the first color.
Rolls are arranged, ethylene-vinyl alcohol copolymer
Water (ethylene content: 29 mol%) and n-p
1% 15% solution in propyl alcohol (1/1) solvent
Use a resin composition consisting of 100 parts by weight,
Coated by an all-coat method, and a thickness of 1.1 g /
m ^Two(Dry state) to form a coating film,
Heat treatment at 120 ° C for 5 minutes to form a coated cured film
Thus, a barrier film was manufactured. Next,
Continue on top of the coating film of the rear film
Using the gravure printing machine described above,
The product was used to form the desired multicolor printed picture layer. Change
Also, an adhesive layer for laminating is formed on the surface of the printed pattern layer.
Done. On the other hand, a non-stretched polypropylene
Prepare a film and apply corona discharge treatment to one side.
And the above-mentioned biaxially stretched nylon
The laminating adhesive layers of the film are opposed to each other.
Layered by dry lamination method
Manufactured.

EXPERIMENTAL EXAMPLE 1 The following data were measured for each of the barrier films and the laminates manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 above. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is a condition of temperature of 40 ° C and humidity of 90% RH in the United States,
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. (3). Measurement of color evaluation This was evaluated by measurement by visual observation of coloring. Coloring observation by visual observation is performed by visually stacking 10 samples.
Observed directly. (4). Measurement of Laminate Strength The laminate was manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 by cutting into a width of 15 mm to produce a test piece, which was then subjected to a tensile tester (Orientec Co., Ltd.). Manufactured). The above measurement results are shown in Table 1 below. Table 1 shows the barrier film, and the measurement results of the oxygen permeability and the water vapor permeability of the laminated material, and the laminate strength of the laminated material. In Table 1, the unit of the oxygen permeability is cm ³ / m ² · d
ay.atm, and the unit of water vapor permeability is g
/ M ² · day · atm, and the unit of the laminating strength is g / 15 mm width.

[0041]

[Table 1]

As is clear from the results shown in Table 1 above.
In addition, the laminated material according to Examples 1 to 6, the oxygen permeability,
0.5cc / m^Two· Day · atm or less. to this
On the other hand, the laminated materials according to Comparative Examples 1 to 3 have an oxygen permeability,
1.2cc / m ^Two・ Day ・ atm or more. Ma
In addition, the laminating strength also depends on Examples 1 to 6.
The laminated material is superior to the laminated materials according to Comparative Examples 1 to 3.
Was. The above results indicate that the laminated materials according to Examples 1 to 6
-Improve oxygen permeability by providing a hardened film
It shows what can be done. Next, water vapor transmission
Regarding the degree, the laminated material according to Examples 1 to 6 is 0.5
g / m^Two・ Day ・ atm or less,
The laminated material according to Comparative Examples 1 to 3 was 1.5 g / m^Two・ Day
-It was atm or more.

[0043]

As is apparent from the above description, the present invention focuses on a vapor-deposited thin film of an inorganic oxide formed by a chemical vapor deposition method and a polymer having high adhesion to a vapor-deposited thin film of an inorganic oxide. First, a vapor-deposited thin film of an inorganic oxide is provided on one surface of the base film by a chemical vapor deposition method, and an ethylene-vinyl alcohol copolymer is further coated on the vapor-deposited thin film of the inorganic oxide. The main component of the vehicle, and at least
Producing a barrier film by providing a coating film of a resin composition containing one or more polymers having high adhesion to the above-mentioned inorganic oxide vapor-deposited thin film,
The barrier film is arbitrarily laminated with another plastic film or a material such as a paper base material or the like to produce a laminated material. To produce a packaging container, for example, in the packaging container, food and drink, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. Improves the tight adhesion of the oxide to the deposited thin film, and has excellent gas barrier properties against oxygen gas and water vapor.
Prevents alteration of contents, modification, etc., has a long-term stable distribution, storage suitability, etc., and also has excellent transparency, so that contents can be visually recognized from the outside. A useful barrier film which is excellent in flexibility, heat resistance, laminating strength, etc., does not have bag breakage, etc. and can produce extremely excellent and excellent packaging products at a low cost; and manufactures a laminate material using the same. It is possible to do.

[Brief description of the drawings]

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

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

FIG. 3 is a schematic configuration diagram of a plasma enhanced chemical vapor deposition apparatus showing an outline of a method of forming a deposited thin film of an inorganic oxide by a chemical vapor deposition method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Barrier film 2 Base film 3 Inorganic oxide vapor-deposited thin film by chemical vapor deposition method 4 Coating film 5 Printing picture layer 6 Heat-sealing resin layer 11 Plasma chemical vapor deposition apparatus 12 Vacuum chamber 13 winding Roll-out roll 14 Auxiliary roll 15 Cooling / electrode drum 16 Gas supply device 17 Gas supply device 18 Raw material volatile supply device 19 Raw material supply nozzle 20 Glow discharge plasma 21 Power supply 22 Magnet 23 Auxiliary roll 24 Take-up roll Le 25 vacuum pump

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B32B 18/00 B32B 18/00 C 4F100 27/28 102 27/28 102 4K030 27/32 27/32 Z 27 / 34 27/34 27/36 27/36 B65D 65/40 B65D 65/40 D C08J 3/24 C08J 3/24 A 7/00 306 7/00 306 7/04 7/04 PL 7/06 CES 7 / 06 CESZ CFD CFDZ CFG CFGZ C23C 16/40 C23C 16/40 F term (reference) 3E086 AD01 AD02 BA04 BA15 BA24 BA40 BB01 BB22 BB41 CA01 CA11 CA28 CA29 CA35 4D075 CA13 CA18 CA42 CB06 DA04 DB36 DB48 DC36A13 A05 AA17 AA18 AA19 AA22 AA35 AA36 AA38 AB12 AB20 AB32 AB67 AB76 BA05 BA13 CA07 DA01 DA03 DA04 EA05 4F070 AA13 AA26 AC54 AC74 AC90 AE22 AE30 GA01 GA06 GC02 GC08 GC09 4F073 AA17 BA0 8 BA24 BA29 BB01 BB09 CA02 CA70 GA11 HA15 4F100 BA03 BA04 BA07 BA26 CB02 GB15 JD03 JD04 JJ03 JK06 JK17 JN01 4K030 AA06 AA09 BA42 BA44 CA07 CA12 DA02 FA01 GA14 JA01 LA01 LA11 LA24

Claims (10)

[Claims] 1. An inorganic oxide vapor-deposited thin film formed by chemical vapor deposition on one surface of a substrate film, and an ethylene-vinyl alcohol copolymer is further provided on the inorganic oxide vapor-deposited thin film. Is a main component of a vehicle, and at least a coating film made of a resin composition containing one or more polymers having high adhesion to the vapor-deposited thin film of the inorganic oxide is provided. Characteristic barrier film. 2. The barrier film according to claim 1, wherein the base film comprises a biaxially oriented polypropylene film, a biaxially oriented polyethylene terephthalate film, or a biaxially oriented nylon film. . 3. The barrier according to claim 1, wherein the vapor-deposited inorganic oxide thin film formed by chemical vapor deposition comprises a vapor-deposited inorganic oxide thin film formed by plasma chemical vapor deposition. Film. 4. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film formed by chemical vapor deposition comprises a silicon oxide vapor-deposited thin film formed by plasma chemical vapor deposition. Barrier film. 5. The method according to claim 1, wherein the vapor-deposited thin film of the inorganic oxide formed by the chemical vapor deposition method comprises a vapor-deposited thin film of silicon oxide formed by a plasma-enhanced chemical vapor deposition method using an organosilicon compound as a monomer gas for the vapor deposition. The barrier film according to claim 1, 2 or 3, wherein 6. A vapor-deposited thin film of an inorganic oxide formed by a chemical vapor deposition method has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, any one of carbon (C) and hydrogen (H) is used. On the other hand, or consists of a vapor-deposited thin film of silicon oxide containing both elements as trace elements, and the film thickness is
The angle is in the range of 50 ° to 500 °, and the composition ratio of the essential constituent element and the trace constituent element continuously changes in the film thickness direction.
6. The barrier film described in 2, 3, 4 or 5. 7. The barrier property according to claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%. the film. 8. The method according to claim 1, wherein the polymer having high adhesiveness to the deposited inorganic oxide thin film comprises at least one of a polyethyleneimine-based polymer, a polycarbodiimide-based polymer, and a polyvinylpyrrolidone-based polymer. The barrier film according to claim 1, 2, 3, 4, 5, 6, or 7, which is characterized by the following. 9. The method according to claim 1, wherein the resin composition contains a silane coupling agent.
9. The barrier film described in 5, 6, 7 or 8. 10. A vapor-deposited thin film of an inorganic oxide formed by chemical vapor deposition on one surface of a substrate film, and an ethylene-vinyl acetate copolymer is further deposited on the vapor-deposited thin film of an inorganic oxide. A coating film made of a resin composition containing a saponified material as a main component of a vehicle and at least one or more polymers having high adhesion to at least the above-mentioned vapor-deposited thin film of an inorganic oxide. A laminated material characterized in that at least a heat-sealing resin layer is provided on the surface of the coating cured film of the provided barrier film.