JP2000117879A - Barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film enhanced in the close adhesiveness with a vapor deposition film of inorg. oxide, enhanced in gas barrier properties to oxygen gas and steam and enhanced 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 vapor deposition membrane 4 of inorg. oxide due to a physical gas phase growing method is provided on the vapor deposition membrane 3 of inorg. oxide and a coating film 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 4 of inorg. oxide and a laminated 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 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 is formed favorably by a vacuum vapor deposition method or the like, and the effect such as gas barrier property against oxygen gas and the like is obtained. Can be improved. However, when using 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, forming a vapor-deposited film by a vacuum vapor deposition method or the like is not suitable. Although it is possible, it is difficult to improve the effects such as the gas barrier property of oxygen gas or the like, and it cannot be said that it is always 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. Further, it has been proposed to further improve the gas barrier property, but the tight adhesion between the deposited film and the coating film or the laminated film made of the barrier resin is poor, and the laminating suitability is lacking. Phenomenon occurs, and it is capable of sufficiently satisfactory is the actual situation that not say. Therefore, the present invention improves the close adhesion of the inorganic oxide to the vapor-deposited film, has excellent gas barrier properties against oxygen gas and water vapor gas, and has further improved transparency, heat resistance, flexibility, and laminating suitability. An object of the present invention is to provide an excellent barrier film 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 an inorganic oxide vapor-deposited thin film by chemical vapor deposition and an inorganic oxide by physical vapor deposition. Focusing on a polymer having a high adhesion between a vapor-deposited thin film of an oxide and a vapor-deposited thin film of an inorganic oxide, first, a vapor-deposited thin film of an inorganic oxide formed by chemical vapor deposition on one surface of a substrate film. Is further provided on the vapor-deposited thin film of inorganic oxide, and a vapor-deposited thin film of inorganic oxide is provided on the vapor-deposited thin film of inorganic oxide by physical vapor deposition. A coating film of a resin composition containing a copolymer as a main component of a vehicle and at least one or more polymers having high adhesion to a vapor-deposited thin film of the above-described inorganic oxide is provided. To produce a barrier film, and A laminated film is manufactured by arbitrarily laminating a material such as another plastic film or a paper base material or the like on the rear film, and then using the laminated material, bag-forming or box-forming the laminated material. To produce a packaging container, in the packaging container, for example, food and drink, pharmaceuticals, chemicals,
Various products such as daily necessities, miscellaneous goods, etc. were filled and packaged to produce a packaged product, which improved the tight adhesion with the inorganic oxide vapor-deposited thin film, and had 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 good packaging products at low cost, and a laminated material using the same. Thus, the present invention has been completed.

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. A vapor-deposited thin film of an inorganic oxide is provided by a method, and an ethylene-vinyl alcohol-
And a coating film of a resin composition containing at least one polymer having high adhesion to at least the above-mentioned vapor-deposited thin film of an inorganic oxide. The present invention relates to a barrier film provided and a laminate 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, on the inorganic oxide vapor-deposited thin film 3, an inorganic oxide vapor-deposited thin film 4 is provided by physical vapor deposition, and on the inorganic oxide vapor-deposited thin film 4, ethylene-vinyl alcohol is further deposited. Coating film 5 made of a resin composition containing a copolymer 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 4 of an inorganic oxide. Is provided as a basic structure. Next, the laminated material 1 according to the present invention
As a, as shown in FIG. 2, a printing pattern layer 6 is provided on the surface of the coating film 5 constituting the barrier film 1 shown in FIG. 6
The basic structure is that at least a heat-sealing resin layer 7 is provided on the entire surface including the above.
In FIG. 2, reference numerals 2, 3, 4 and the like 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-mentioned laminated material, other plastic films, paper substrates, etc. are arbitrarily laminated at desired positions according to the contents to be filled and packaged, the purpose of use, and the like. Materials can be manufactured.

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 substrate film 2 conveyed on the cooling / electrode drum 15 peripheral surface, and the plasma is irradiated to deposit the inorganic oxide such as silicon oxide. A thin film is formed and formed into a film. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 15 from a power source 21 disposed outside the chamber, and a magnet 22 is provided near the cooling / electrode drum 15. Then, the base film 2 on which the deposited thin film of the inorganic oxide such as silicon oxide is formed is wound up through the auxiliary roll 23 and the roll 24 is formed. 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, 25
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 organosilicon compound and oxygen gas, and the reaction product is closely adhered to the substrate film. and dense, it is possible to form a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Represents a number of 0 to 2). Thus, the above-mentioned vapor-deposited thin film of silicon oxide is represented by the general formula SiO _X (where X represents a number of 1.3 to 1.9) from the viewpoint of transparency, barrier properties and the like. It is preferably a thin film mainly composed of a deposited silicon oxide film. 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, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has 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 further has one of carbon (C) and hydrogen (H);
Alternatively, it is composed of a deposited film of silicon oxide containing both elements as trace constituent elements and has a thickness of 50 °.
And the constituent ratio between the essential constituent elements and the trace constituent elements changes continuously in the film thickness direction. 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,
Regarding the above-mentioned silicon oxide vapor-deposited thin film, for example, an X-ray photoelectron spectrometer (Xray Photoelectron)
Spectroscopy, XPS), Secondary Ion Mass Spectrometer (Secondary Ion Mass S)
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide thin film using a method of analyzing the surface by ion etching in the depth direction using a surface analyzer such as a Spectroscopy (SIMS). Is what you can do. In the present invention, the thickness of the deposited silicon oxide thin film is desirably 500 ° or less, and specifically, the thickness is 50 to 5 mm.
The position is preferably around 00 °, more preferably around 100 to 300 °.
If the thickness is greater than 0 °, cracks and the like are likely to occur in the film, which is not preferable.
If it is less than Å, it is not preferable because it is difficult to exhibit the effect of the barrier property. In the above,
The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Also,
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, increasing the amount of the monomer gas and the oxygen gas or reducing the deposition rate It can be performed by a method 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 is long and the base film is deteriorated.
It is preferable to form a deposited film at a deposition rate of 200 to 200 n / min.

Next, in the present invention, the vapor-deposited thin film of the inorganic oxide formed by the physical vapor deposition method constituting the barrier film or the laminated material according to the present invention will be described. For example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion plating method (Physi
cal Vapor Deposition method, PVD
Method) to form a deposited thin film of an inorganic oxide. In the present invention, specifically, a metal oxide is used as a raw material, and a vacuum evaporation method in which the metal oxide is heated and vapor-deposited on a base film, or a metal or a metal oxide is used as a raw material, and oxygen is used. The vapor deposition film can be formed by an oxidation reaction vapor deposition method of introducing and oxidizing and vapor-depositing on the substrate film, and a plasma-assisted oxidation reaction vapor deposition method of promoting the oxidation reaction by plasma. In the present invention, a specific example of a method of forming a thin film of an inorganic oxide by physical vapor deposition is shown in FIG. 4. FIG. 4 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 4, in a vacuum chamber 52 of a take-up type vacuum deposition apparatus 51, a base film 2 having a deposited thin film of an inorganic oxide by a chemical vapor deposition method unwound from an unwinding roll 53 is formed. , Are guided to a cooled coating drum 56 via guide rollers 54 and 55. Thus, the crucible 57 is placed on the deposited inorganic oxide thin film of the base film 2 having the deposited inorganic oxide thin film formed by chemical vapor deposition guided on the cooled coating drum 56.
A deposition source 58 heated at, for example, metal aluminum,
Alternatively, aluminum oxide or the like is evaporated, and if necessary, oxygen gas or the like is ejected from the oxygen gas outlet 59,
While supplying this, through a mask 60, 60, for example, a deposited thin film of an inorganic oxide such as aluminum oxide is formed, and then, in the above, for example, a deposited thin film of an inorganic oxide such as aluminum oxide is formed. The base film 2 formed on the inorganic oxide vapor-deposited thin film by the above-described chemical vapor deposition method is sent out through guide rolls 55 'and 54', and wound up on a take-up roll 61. An inorganic oxide vapor-deposited thin film can be formed by the physical vapor deposition method according to the present invention.

In the above, as the inorganic oxide deposited thin film, basically any thin film on which a metal oxide is 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.

Next, in the present invention, the barrier film according to the present invention or the ethylene-vinyl alcohol copolymer constituting the laminate is used as a main component of the vehicle,
This and at least a coating film made of a resin composition containing one or more polymers having high adhesion to a vapor-deposited thin film of an inorganic oxide will be described. As such a coating film, for example, One or more ethylene-vinyl alcohol copolymers are used as the main component of the vehicle, and at least one of the above polymers having high adhesion to the deposited thin film of inorganic oxide by the physical vapor deposition method described above.
One or more of the following, and further, if necessary, for example, a light stabilizer such as a filler, a stabilizer, a plasticizer, an antioxidant, an ultraviolet absorber, a dispersant, a thickener, a drying agent, Lubricant, antistatic agent, cross-linking agent, optionally add other additives such as,
Solvent type, aqueous type, sufficiently kneaded with solvent, diluent, etc.
Alternatively, a resin composition composed of an emulsion type or the like is prepared, and the resin composition is used. For example, a roll coat method, a gravure roll coat method, a kiss roll coat method, -Coating amount, for example, 0.1 g / m ^2- by coating method such as roll coating method, reverse roll coating method, curtain flow coating method and others.
About 10 g / m ² (dry state), preferably 0.5 g / m ²
The coated film is coated so as to have a m ^{2 to 5} g / m ² (dry state), and then heated and dried, and further subjected to an aging treatment to form a coated cured film according to the present invention. be able to. In the above, as the above-mentioned resin composition, an ethylene-vinyl alcohol copolymer, a polymer or the like having high adhesion to a vapor-deposited thin film of an inorganic oxide is dissolved or kneaded, and further, the films are cured. For this reason, it is preferable to use a resin composition prepared using an alcohol-water-based solution or the like. Thus, as the alcohol component, for example, n-propyl alcohol, isopropyl alcohol -N-butanol, t-butanol,
Ethyl alcohol, methyl alcohol and the like can be used, and in the above-mentioned alcohol-water solution,
The mixing ratio of alcohol to water is preferably, for example, 50 to 30 parts by weight of water to 50 to 70 parts by weight of alcohol to adjust the alcohol-water 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.

Further, in the above, as the polymer having a good adhesion to the vapor-deposited thin film of the inorganic oxide by the physical vapor deposition method, for example, a polyethyleneimine-based polymer,
One or more of polycarbodiimide-based polymers and polyvinylpyrrolidone-based polymers can be used. Specifically, the polyethyleneimine-based polymer includes, for example, N
-Unsubstituted polyalkyleneimine, N-alkyl-substituted polyalkyleneimine, N-acyl-substituted polyalkyleneimine and the like can be used, and as the above polycarbodiimide-based polymer, for example, polycarbodiimide and the like are used Further, as the polyvinylpyrrolidone-based polymer, for example, polyvinylpyrrolidone, polyalkylated vinylpyrrolidone, a copolymer of vinylpyrrolidone and vinyl acetate, a copolymer of vinylpyrrolidone and styrene and the like are used can do. 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 it is not clear.
A carbodiimide group, an imine group, a pyrrolidone group, etc., are hydroxyl groups in an ethylene-vinyl alcohol copolymer,
In addition, by causing an interaction such as a hydrogen bond with each of the inorganic oxide vapor-deposited thin films, the adhesiveness between the ethylene-vinyl alcohol copolymer and the inorganic oxide vapor-deposited thin films is improved. It is estimated that 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. Copolymer 100
The blending ratio of 0.1 to 100 parts by weight of the polymer, which is rich in close adhesion to the deposited thin film of the inorganic oxide, is preferably based on parts by weight.

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, and to improve the tight adhesion between the coating film and the inorganic oxide vapor-deposited thin film formed by the physical vapor deposition method. A barrier film composed of three layers, ie, two layers of inorganic oxide vapor-deposited thin films and one layer of a coating film by a growth method and a physical vapor deposition method, further improves the barrier properties against oxygen gas or water vapor gas. To do It is those estimated to that. Furthermore, in the present invention, in the resin composition according to the present invention, by adding a silane coupling agent having the above-described binary reactivity, an ethylene-vinyl alcohol copolymer, or an inorganic oxide. A polymer or the like having a high degree of close adhesion to the deposited thin film forms a three-dimensionally networked coating film via the silane coupling agent and the like to further improve the close adhesion to the deposited thin film of inorganic oxide. It can improve the barrier properties against oxygen gas, water vapor, and the like, as well as improve it.

Next, in the present invention, as the print pattern layer constituting the laminate 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. 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.

Next, 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.

By the way, in the laminated material according to the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, the laminated material constituting the packaging container is severe. Packaging suitability is required, and various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. In the present invention, a material that satisfies the above-described conditions is arbitrarily selected and used. In addition to the above-described materials constituting the laminate according to the present invention, these materials are further arbitrarily added and laminated. Thus, a desired laminated material can be formed. 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 laminate according to the present invention produced as described above is a temperature of 23 ° C. and a relative humidity of 90% R
In H, it has an extremely excellent effect of not more than 0.4 cc / m ² · day · atm. The above-mentioned measurement of oxygen permeability is carried out by using, for example, the above-mentioned oxygen permeability measuring instrument [model name, Oxtran (OX-TRAN) 2/20] manufactured by MOCON, USA, 23
It can be measured under the conditions of ° C. and 90% RH.

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 using it to form 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.

[0032]

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.
Using an axially stretched polyethylene terephthalate film,
This is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and is fed out onto a coating drum. Under the following conditions, aluminum is used as an evaporation source, and while supplying oxygen gas, an electron beam is supplied. A 200 ° -thick aluminum oxide film is deposited on the silicon oxide vapor-deposited thin film of the biaxially stretched polyethylene terephthalate film on which the silicon oxide vapor-deposited film is formed by a reactive vacuum vapor deposition method using a heating (EB) heating method. A thin film was formed. (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 / Minutes (3). Next, a biaxially stretched polyethylene terephthalate film on which an aluminum oxide vapor-deposited thin film was formed as described above was used, and a gravure printer was used on the aluminum oxide vapor-deposited thin film surface, and a gravure coat was applied to the first color. And 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 placed in one roll.
A resin composition was prepared by adding 20 parts by weight of a 5% solution of polyethyleneimine (manufactured by Nippon Shokubai Kagaku Co., Ltd.) to 00 parts by weight, and this was coated by a gravure roll coating method.
To a 1.1 g / m ² (dry state) core
A coating film 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. (4). 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.
An axially stretched polypropylene film was used, which was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, which was unwound onto a coating drum. The same evaporation conditions as described in Example 1 above were used. The silicon oxide of the biaxially stretched polypropylene film on which a deposited thin film of silicon oxide was formed by a reactive vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas while using aluminum as a deposition source. Was formed on the above deposited thin film of aluminum oxide. (3). Next, a gravure coat roll is placed on the first color of the biaxially stretched polypropylene film on which the aluminum oxide vapor-deposited thin film is formed by using a gravure printing machine on the aluminum oxide vapor-deposited thin film surface. , Ethylene-
Ion-exchanged water of vinyl alcohol copolymer (ethylene content 32 mol%) and n-propyl alcohol (1 /
1) 5 parts of a 15% solution of polycarbodiimide (manufactured by Nisshinbo Co., Ltd.) was added to 100 parts by weight of a 15% solution of a solvent.
A resin composition to which a part by weight was added was used, and this was coated by a gravure roll coating method to obtain a resin composition having a thickness of 1.1 g /
forming a coating film of m ² (dry state);
A coating cured film was formed by heat treatment at 120 ° C. for 5 minutes to produce 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. (4). 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.
An axially stretched nylon film was used, which was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and was fed out onto a coating drum. The same conditions as the evaporation conditions described in Example 1 above were used. Then, an electron beam (E) is used while supplying oxygen gas using aluminum as a deposition source.
B) A 200-mm-thick aluminum oxide vapor-deposited thin film was formed on the silicon oxide vapor-deposited thin film of the biaxially stretched nylon film having the silicon oxide vapor-deposited thin film formed thereon by a reactive vacuum vapor deposition method using a heating method. (3). Next, using a gravure printing machine, a gravure coat roll was placed on the first color of the biaxially stretched nylon film on which the vapor deposited thin film of animinium oxide was formed, using a gravure printing machine. A 15% solution of ethylene-vinyl alcohol copolymer (ethylene content 29 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent is 100 parts by weight, and 10% by weight of polyvinylpyrrolidone A resin composition prepared by adding 5 parts by weight of the solution is coated by a gravure roll coating method to form a coating film having a thickness of 1.1 g / m ² (dry state). Then, heat treatment was performed at 120 ° C. for 5 minutes to form a cured coating film, thereby producing a barrier film according to the present invention. Next, on the coating cured film of the barrier film, subsequently, using the gravure printing machine described above, using a gravure ink composition,
The desired multicolor printed picture layer was formed. (4). 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 the printed picture layer surface is cured with a two-part coating using a gravure roll coating method. An adhesive for a polyurethane type laminate was applied at a rate of 4.5 g / m ² (dry weight) to form an adhesive layer for a laminate. 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.

Example 4 In (4) 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 (4) 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 the above (3) of Example 3, a 70 μm thick non-coated film was formed on the printed pattern layer surface of the biaxially stretched nylon film having the 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 base material, and one side of the biaxially stretched polyethylene terephthalate film was applied in the same manner as in Example 1 above. Then, a deposited thin film of silicon oxide was formed, and then a deposited thin film of aluminum oxide was formed. Next, a gravure coat roll was placed on the first color of the aluminum oxide vapor-deposited thin film surface using a gravure printer in the same manner as in Example 1 to obtain an ethylene-vinyl alcohol.
Of ethylene copolymer (ethylene content 32 mol%) with ion-exchanged water and n-propyl alcohol (1/1) solvent
% Solution is used and coated by a gravure roll coating method to form a coating film having a thickness of 1.1 g / m ² (dry state). Then, a heat treatment was performed at 120 ° C. for 5 minutes to form a coating cured film, thereby producing a barrier film. Next, on the coating cured film of the barrier film, subsequently, in the same manner as in Example 1, using the gravure printing machine described above, using a gravure ink composition,
A desired multicolor print pattern layer was formed, and then an adhesive layer for laminating was formed on the print pattern layer surface. 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 a silicon oxide deposited thin film was formed on one surface of the biaxially oriented polypropylene film in the same manner as in Example 2 above. Was formed, and then a deposited thin film of aluminum oxide was formed. Next, a gravure coating roll was placed on the first color of the aluminum oxide vapor-deposited thin film surface in the same manner as in Example 2 above, and ethylene-vinyl alcohol was used. A resin composition consisting of 100 parts by weight of a 15% solution of a copolymer (ethylene content 32 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent was used. −
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, on the coating cured film of the barrier film, using the gravure printing machine described above and the gravure ink composition in the same manner as in Example 2 above, the desired amount A color print pattern layer was formed, and then an adhesive layer for laminating was formed on the print pattern layer surface. 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 A biaxially stretched nylon film having a thickness of 15 μm was used as a substrate, and a thin film of silicon oxide was deposited on one surface of the biaxially stretched nylon film in the same manner as in Example 3 above. Was formed, and then a deposited thin film of aluminum oxide was formed.
Next, a gravure coat roll was placed on the first color of the aluminum oxide vapor-deposited thin film surface using a gravure printer in the same manner as in Example 3 above.
Ion-exchanged water of a vinyl alcohol copolymer (ethylene content: 29 mol%) and n-propyl alcohol (1/1)
1) A resin composition consisting of 100 parts by weight of a 15% solution in a solvent was used, and this was coated by a gravure roll coating method.
To a 1.1 g / m ² (dry state) core
A coating film was formed and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film, thereby producing a barrier film. Next, on the coating cured film of the barrier film, using the gravure printing machine described above and the gravure ink composition in the same manner as in Example 3 described above, A color print pattern layer was formed, and then an adhesive layer for laminating was formed on the print pattern layer surface. On the other hand, a non-stretched polypropylene film having a thickness of 70 μm was prepared, and one surface thereof was subjected to a corona discharge treatment,
The laminating adhesive layer surface of the biaxially stretched polypropylene film was opposed to the corona discharge treated surface, and both were laminated by dry lamination to produce a laminated material.

EXPERIMENTAL EXAMPLE 1 The following data were measured for each of the barrier films and laminated materials produced 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 This was performed by using the laminated materials manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 to prepare a test piece having a width of 15 mm therefrom, and using a tensile tester (manufactured by Orientec Co., Ltd.) Was measured by The above measurement results are shown in Table 1 below. Table 1
It is a measurement result of the oxygen permeability and the water vapor permeability of the barrier film and the laminated material, and the laminate strength of the laminated material. In Table 1, the unit of oxygen permeability is cm ³ / m ² · day · atm, and the unit of water vapor permeability is g / m ² · day · atm.
Yes, and the unit of laminate strength is g / 15mm
It is width.

[0042]

[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,
0.4cc / 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, regarding the laminating strength, according to 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.

[0044]

As is apparent from the above description, the present invention provides a method for depositing a thin film of an inorganic oxide by a chemical vapor deposition method, a method of depositing a thin film of an inorganic oxide by a physical vapor deposition method, Focusing on polymers with high adhesion to vapor-deposited thin films,
First, a vapor-deposited thin film of an inorganic oxide is provided on one surface of a base film by a chemical vapor deposition method, and further, a vapor-deposited inorganic oxide is deposited on the vapor-deposited thin film of the inorganic oxide by a physical vapor deposition method. A thin film is provided, and an ethylene-vinyl alcohol copolymer is used as a main component of a vehicle on the vapor-deposited thin film of the inorganic oxide, and is tightly adhered to at least the vapor-deposited thin film of the inorganic oxide. A barrier film is manufactured by providing a coating film made of a resin composition containing one or more polymers having high properties, and the barrier film is replaced with another plastic film or paper base. Materials, and other materials are arbitrarily laminated to produce a laminated material, and then
Using the laminated material, it is made into a bag or a box to produce a packaging container, and in the packaging container, for example, various kinds of foods and drinks, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. Filling and packaging products to produce packaging products, improve the tight adhesion of inorganic oxides to the deposited thin film, and have excellent gas barrier properties against oxygen gas and water vapor, etc. It has stable long-term distribution and storage suitability, and is excellent in transparency, so that the contents can be visually recognized from the outside, and further, flexibility, heat resistance and laminating properties.
A useful barrier film which is excellent in strength and the like, has no bag breakage and the like, and is capable of producing an extremely excellent and excellent packaged product at a low cost, and a laminate material using the same can be produced.

[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.

FIG. 4 is a schematic configuration diagram of a roll-up type vacuum deposition apparatus showing an outline of a method of forming a deposited thin film of an inorganic oxide by a physical vapor deposition method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Barrier film 2 Substrate film 3 Deposited thin film of inorganic oxide by chemical vapor deposition method 4 Deposited thin film of inorganic oxide by physical vapor deposition method 5 Coating film 6 Printed pattern layer 7 Heat sealing property Resin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 18/00 B32B 18/00 C 4K030 27/28 102 27/28 102 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 14/08 C23C 14/08 A 16/40 16/40 F term (reference) 3E086 AD01 AD02 BA04 BA15 BA40 BB01 BB22 BB41 BB90 CA01 CA11 CA35 4F006 AA12 AA15 AA17 AAA AAA AAA AA AAA AB14 AB15 AB16 AB20 AB23 AB24 AB32 AB35 AB37 AB38 AB74 AB76 BA05 BA13 CA07 DA01 DA03 DA04 EA05 4F070 AA13 AA26 AA38 AA55 AA57 AB11 AB21 AC54 AC90 AE08 GA01 GC02 GC09 4F073 AA17 BA08 BA24 CA02 CA70 EA01 EA65 HA10 4K029 AA11 AA25 BA44 BA46 BB02 BC00 EA01 GA03 4K030 AA11 BA43 BA44 BB13 CA07 CA12 DA08 JA01

Claims (11)

[Claims] 1. An inorganic oxide vapor-deposited thin film formed by chemical vapor deposition on one surface of a substrate film, and an inorganic oxide deposited by physical vapor deposition on the inorganic oxide vapor-deposited thin film. A vapor-deposited thin film of a product is provided, and on the vapor-deposited thin film of the inorganic oxide, an ethylene-vinyl alcohol copolymer is used as a main component of a vehicle. A barrier film provided with a coating film made of a resin composition containing one or more polymers having high adhesion. 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 barrier property 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. the 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 any one of claims 1 to 4, 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.
5. The barrier film according to 5. 7. The barrier film according to claim 1, wherein the vapor-deposited inorganic oxide thin film formed by physical vapor deposition comprises a vapor-deposited inorganic oxide thin film formed by vacuum vapor deposition. 8. The barrier film according to claim 1, wherein the vapor-deposited inorganic oxide thin film formed by physical vapor deposition comprises a vacuum-deposited aluminum oxide vapor-deposited thin film. 9. The barrier film according to claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%. 10. A polymer having a high adhesion to a deposited thin film of an inorganic oxide, comprising one or more of a polyethyleneimine-based polymer, a polycarbodiimide-based polymer, and a polyvinylpyrrolidone-based polymer. The barrier film according to any one of claims 1 to 9, wherein: 11. A vapor-deposited inorganic oxide thin film formed by chemical vapor deposition on one surface of a substrate film, and an inorganic oxide deposited by physical vapor deposition is further formed on the inorganic oxide vapor-deposited thin film. A vapor-deposited thin film of the product is provided, and on the vapor-deposited thin film of the inorganic oxide, a saponified product of an ethylene-vinyl acetate copolymer is used as a main component of the vehicle. Polymer with high adhesion to deposited thin film
A laminate comprising at least a heat-sealing resin layer provided on a coating film surface of a barrier film provided with a coating film of a resin composition containing at least one of the following. Wood.