JP2000127286A - Barrier film and laminate employing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film and a laminate, employing the same, improved in an air-tight adhering property between the deposited film of an inorganic oxide and prominent in gas barrier property with respect to oxygen gas, steam or the like as well as transparency, heat resistant property, flexibility, laminating strength and the like. SOLUTION: An inorganic oxide deposited thin film 4, deposited through chemical gas phase epitaxial method, is provided on one side of a substrate film 2, and, further, an inorganic oxide deposited thin film 4, deposited through physical gas phase growing method, is provided on the inorganic oxide deposited thin film 3, then, a plasma treated surface 5, treated by gas consisting of one kind or two kinds or more of gas of oxygen, nitrogen, argon or helium, is provided on the inorganic oxide deposited thin film 4. Further, a barrier film 1 and the laminate employing the same, in which a coating film 6, produced by a resin composition having ethylene vinyl alcohol copolymer as the principal constituent of the vehicle of the same, is provided on the plasma treated surface 5, are obtained.

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, various materials have been developed and proposed in the past. One of them has recently been applied to one surface of a base film such as a plastic film. For example, using a physical vapor deposition method (PVD method) such as a vacuum deposition method, 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 such as a low-temperature plasma chemical vapor deposition method. For example, a vapor deposition film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide using a vapor deposition method (CVD method) is known. Further, in the above-described vapor-deposited film, in order to further improve the function of blocking oxygen gas or water vapor gas, so-called gas barrier property, on the vapor-deposited film of inorganic oxide, for example, ethylene-vinyl alcohol- A barrier resin such as a vinyl copolymer or a polyvinylidene chloride resin is used to form a coating film or a film laminated film, and a coating film of an inorganic oxide vapor deposition film and a barrier resin is formed. Alternatively, a barrier material formed by forming a two-layer barrier layer with a film laminated film has been proposed. These barrier materials, other plastic film, or paper base, laminated with other materials, such as food and drink, pharmaceuticals, chemicals, daily necessities,
It provides a packaging material useful for packing various goods such as miscellaneous goods and others.

[0003]

However, the above-mentioned barrier materials have oxygen gas barrier properties, water vapor gas barrier properties, and the like, and can be expected to have a certain effect. The fact is that it is not satisfactory. For example, a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of a base film such as the above plastic film using a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method. With respect to the deposited film provided with, a deposited film can be formed on any base film by a vacuum deposition method or the like,
Whether or not it can significantly improve the effects such as gas barrier properties against oxygen gas, water vapor gas, and the like is related to 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 by a vacuum vapor-deposition method or the like, and a gas barrier property against oxygen gas, water vapor gas, and the like is obtained. The effect can be greatly improved. However, for example, when a base film having poor heat resistance such as a biaxially oriented polypropylene film, a non-oriented polypropylene film, or a low-density polyethylene film is used as the base film, it is technically necessary to use a vacuum deposition method or the like. Although it is possible to form a vapor deposition film by, but it is difficult to significantly improve the effects such as gas barrier properties against oxygen gas, water vapor gas, etc., it can be said that it is not necessarily satisfactory. Not something. Further, as the above base film,
For example, when using a polyethylene terephthalate film, the polyethylene terephthalate film is
There is a problem that it has rigidity, is hard, and easily generates wrinkles and the like in the film, and is therefore unsuitable for packaging materials that require flexibility and the like.

Further, one surface of a base film such as the above plastic film is coated with a chemical vapor deposition method (CVD method) such as a low temperature plasma chemical vapor deposition method 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 20 cc / m ² or more, and it can be said that the oxygen gas barrier property that can always be sufficiently satisfied can 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, after forming the above-mentioned inorganic oxide vapor-deposited film, a barrier resin such as ethylene-vinyl alcohol copolymer is used on the inorganic oxide vapor-deposited film. A barrier material composed of a coating film or a film laminate film made of a barrier resin to form a two-layer barrier layer and further improving the gas barrier properties of the barrier material includes a vapor-deposited inorganic oxide film and a barrier layer. It is difficult to say that the resin is not sufficiently satisfactory because of poor adhesion to the coating film or the film laminated film due to the resin, lacking its laminating suitability, and causing phenomena such as delamination. It is. Therefore, the present invention improves the tight adhesion between the inorganic oxide and the deposited film, and has excellent gas barrier properties against oxygen gas and water vapor gas, and furthermore, transparency, heat resistance,
An object of the present invention is to provide a barrier film excellent in flexibility and laminating suitability, and a laminated material using the same.

[0006]

As a result of various studies to solve the above problems, the present inventor has focused on modifying the surface of a deposited thin film of inorganic oxide by physical vapor deposition. First, on one surface of the base film, a vapor-deposited thin film of an inorganic oxide is provided by a chemical vapor deposition method, and further on the vapor-deposited thin film of the inorganic oxide, an inorganic oxide is deposited by a physical vapor deposition method. Is further provided on the vapor-deposited thin film surface of the inorganic oxide by oxygen, nitrogen, argon, or helium.
A plasma treatment with a gas of one or more species is performed to form a plasma treatment surface on the above-mentioned inorganic oxide vapor-deposited thin film surface, and further, an ethylene-vinyl alcohol copolymer is provided on the plasma treatment surface. A barrier film is manufactured by providing a coating film made of a resin composition containing a main component of the above, and any other material such as a plastic film or a paper base material or the like can be used as the barrier film. To produce a laminated material, and then using the laminated material, to produce a packaging container by bag making or box making, in the packaging container, for example, food and beverage, pharmaceuticals, chemicals,
Various products such as daily necessities, miscellaneous goods, etc. were filled and packaged to produce a packaged product, and the tight adhesion between the vapor-deposited thin film of inorganic oxide and the coating film was improved, and its oxygen gas, water vapor, etc. Improves gas barrier properties, prevents alteration, modification, etc. of the contents, has stable long-term distribution, storage suitability, etc., and has excellent transparency, so the contents can be visually recognized from the outside. More 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 the vapor-deposited thin film of an inorganic oxide is further provided on the vapor-deposited thin film of the inorganic oxide Providing a vapor-deposited thin film of an inorganic oxide by a method, and providing a plasma-treated surface with a gas comprising one or more of oxygen, nitrogen, argon, or helium on the vapor-deposited thin film surface of the inorganic oxide, Further, the present invention relates to a barrier film having a coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle, and a laminated material using the same. Things.

[0008]

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, a vapor-deposited inorganic oxide thin film 4 is provided on the vapor-deposited inorganic oxide thin film 3 by physical vapor deposition, and oxygen, nitrogen, argon,
Alternatively, a plasma treatment surface 5 with a gas composed of one or more kinds of helium is provided, and the plasma treatment surface 5 is formed of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle. Coating film 6
Is provided as a basic structure. Next, as shown in FIG. 2, the laminated material 1a according to the present invention is provided on the surface of the coating film 6 constituting the barrier film 1 shown in FIG. And a basic structure comprising at least a heat-sealing resin layer 8 on the entire surface including the printed picture layer 7. In FIG. 2, reference numerals 2, 3, 4, 5, etc. have the same meanings 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 material, material, manufacturing method and the like constituting the barrier film and the laminated material according to the present invention will be described. First, the barrier film or the laminated material according to the present invention will be described. 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 side of the base film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and further, an inert gas such as an argon gas and a helium gas is used. , As an oxygen supply gas,
A vapor-deposited thin film of an inorganic oxide such as silicon oxide can be formed using oxygen gas or the like and low-temperature plasma chemical vapor deposition (CVD) using a low-temperature plasma generator or the like. In the above, as the low-temperature plasma generator, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma or the like can be used, and thus,
In the present invention, in order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

More specifically, a method of forming a vapor-deposited thin film of an inorganic oxide by the above-described low-temperature plasma enhanced chemical vapor deposition method will be described with reference to an example. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an inorganic oxide. As shown in FIG. 3, in the present invention, the base film 2 is unwound from an unwinding roll 13 arranged in a vacuum chamber 12 of a low-temperature plasma chemical vapor deposition apparatus 11, and Material film 2
Is transported onto the cooling / electrode drum 15 peripheral surface at a predetermined speed via the auxiliary roll 14. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatile supply device 18 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and the cooling / electrode drum 15
Plasma is generated by the glow discharge plasma 20 on the base film 2 conveyed on the peripheral surface, and this is irradiated to form a deposited thin film of an inorganic oxide such as silicon oxide, thereby forming a film. . In the present invention, at 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, 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 for 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 using, for example, a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited silicon oxide thin film, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down. In 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. In general, it is preferable to form a vapor deposition film at a vapor deposition rate of 50 to 200 n / min because the time becomes longer and the base film or the like deteriorates.

Next, in the present invention, a vapor-deposited thin film of an inorganic oxide formed by a physical vapor deposition method constituting a barrier film or a 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 plasma-treated surface constituting the transparent barrier film or the laminate according to the present invention will be described. The plasma-treated surface is used to ionize gas by arc discharge. A plasma-treated surface can be formed by utilizing a plasma surface treatment method for performing surface modification using a plasma gas generated by the method. That is, in the present invention,
A plasma treatment surface can be formed by performing plasma treatment by a method using a gas such as an oxygen gas, a nitrogen gas, an argon gas, or a helium gas as a plasma gas. Thus, in the present invention, the plasma processing includes:
At the time of the plasma discharge treatment, it is preferable to perform the plasma treatment using an oxygen gas or a mixed gas of an oxygen gas and an argon gas or a helium gas. With such a plasma treatment, the plasma treatment is performed at a lower voltage. This makes it possible to prevent deterioration of the deposited thin film of the inorganic oxide, etc., and to provide a favorable plasma-treated surface on the surface.

In the present invention, it is most preferable that the plasma treatment is performed by using a mixed gas of oxygen gas and argon gas or helium gas. It is desirable to perform the process in-line immediately after forming the deposited thin film of the object. That is, in the present invention, on the surface of the inorganic oxide deposited thin film, for example, immediately after its formation, and before the deposited thin film comes into contact with a guide roll or the like,
By performing in-line plasma treatment, impurities, dust and the like adhering to the surface of the deposited thin film of inorganic oxide are removed, and furthermore, a hydrocarbon group (for example, C -C, CH, C =
Etc.) and the degree of oxidation of the surface increases, and a large number of carboxyl groups, keto groups, aceto groups, OH groups, etc. are formed on the surface, and the surface wettability is greatly improved, and Post-processing suitability such as close adhesion, printability and coating property is improved. Thus, in the present invention, a coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle is provided on the above-mentioned plasma-treated surface, as described later. Thereby, it is possible to form a laminated material having high tight adhesion, excellent laminating strength, etc., and a barrier film composed of three layers of a vapor-deposited thin film of inorganic oxide and a coating film. It has a sufficiently high barrier property against oxygen gas, water vapor and the like, and can be used to produce laminated materials having various forms. In addition, in the present invention, since the adhesiveness is excellent and the laminating strength can be increased, for example, in the post-processing such as film winding, printing, laminating, or bag making. In addition, cracks and the like can be prevented from being formed in the above-mentioned inorganic oxide vapor-deposited thin film, and so-called post-processing suitability can be improved. Further, in the present invention, since the plasma treatment is performed in-line, the production cost of the transparent barrier film is extremely excellent.

In the present invention, in the above-described plasma processing, plasma processing conditions are extremely important.
The effect obtained by the condition is completely different. Thus, in the present invention, factors affecting the plasma processing and the chemical reaction include plasma output, gas type, gas supply amount, processing time, and the like. In the present invention, as the plasma treatment, specifically, it is desirable to use a mixed gas of oxygen gas and argon gas or helium gas, and a gas mixture of oxygen gas and argon gas or helium gas. The pressure is preferably about 1 to 1 × 10 ⁻⁴ mbar, more preferably about 1 × 10 ⁻⁴ mbar.
It is desirably about × 10 ⁻¹ to 1 × 10 ⁻³ mbar, and the ratio of oxygen gas to argon gas or helium gas is argon gas or helium gas: oxygen gas = 1: 1 to 1:10 in partial pressure ratio. Position, more preferably 1: 2
1: 6 is desirable, and the plasma output is about 0.3 to 20 kW, more preferably 0.5 to 1 kW.
5 kW is desirable, and the processing speed is about 50 to 500 m / min, more preferably 10 to 500 m / min.
A range of 0 to 400 m / min is desirable. In the above partial pressure ratio of oxygen gas and argon gas or helium gas,
When the partial pressure of argon gas or helium gas increases, oxygen molecules activated by plasma decrease, and argon gas or helium gas acts as a reducing gas, forming an oxide film on the deposited thin film surface of the inorganic oxide, or This is not preferred because the introduction of a hydroxyl group or the like is inhibited. Further, the plasma output is less than 0.5 kW,
Further, when the power is less than 0.3 kW, the activation of the oxygen gas is reduced, and it is difficult to generate highly active oxygen atoms, which is not preferable.
If it exceeds kW, the plasma output is too high, so that cracks and the like tend to occur due to the deterioration of the deposited thin film of the inorganic oxide, which is not preferable because it causes a problem that the physical properties of the transparent barrier film itself deteriorate. is there. Further, when the above processing speed is 400 m / min or more, furthermore, 500 m / min or more, the amount of oxygen plasma is small, and less than 50 m / min.
If it is less than 30 m / min, the deterioration of the deposited thin film of the inorganic oxide or the like proceeds rapidly, and the barrier property is deteriorated, which is not preferable.

In the present invention, as a method of generating plasma in the plasma processing, for example, DC glow discharge, high frequency (Audio Frequ
ency: AF, Radio Frequency: R
F) It can be performed using three types of devices such as discharge and microwave discharge. Thus, in the present invention, it can be usually carried out using a 13.56 MHz high frequency (AF) discharge device.

In the present invention, a plasma-treated surface formed by the above-described plasma treatment on the surface of the deposited inorganic oxide thin film may be, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Spec).
Troscopy, XPS), secondary ion mass spectrometer (Secondary Ion Mass Spect)
roscopy, SIMS), etc.
By analyzing the plasma processing section using a method of performing analysis by ion etching in the depth direction or the like, impurities and dust are removed as described above, and furthermore, the processing surface is thinned. Plasma-treated surface on which an oxide film having high smoothness is formed, and further, for example, a hydroxyl group (-OH
It can be confirmed that the surface is a plasma-treated surface on which a functional group such as a group is formed. In particular,
MgKα1.2 as X-ray source, 15K as X-ray output
XPS analysis of the surface to 100 ° is performed under the measurement conditions of v and 20 mA, and the treatment state can be confirmed by measuring the element ratio of Si, C, O and the like. In the present invention, the surface free energy of the deposited thin film can be measured using a wetting reagent. In the present invention, the surface free energy
Is less than 45 dynes / cm, good close adhesion cannot be obtained, and the surface free energy becomes less than 45 dynes / cm.
Ne / cm, in particular, 50 dyne / cm or more is preferable from the viewpoint of obtaining good tight adhesion.

Next, in the present invention, a coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle, which constitutes a barrier film or a laminated material according to the present invention, will be described. Then
As such a coating film, for example, one or more ethylene-vinyl alcohol copolymers are used as a main component of a vehicle, and further, if necessary, for example,
Optional additives such as fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc. And solvent,
A resin composition composed of a solvent type, an aqueous type, an emulsion type or the like which is sufficiently kneaded with a diluent or the like is prepared, and the resin composition is used, for example, by a roll coating method. Gravure roll coating, kiss roll coating, squeeze roll coating, reverse roll coating, curtain flow coating, and other coating methods. , Coating amount, for example, 0.1 g / m ^{2 to} 10 g
/ M ² (dry state), preferably 0.5 g / m ² to
Coating is performed so as to be about 5 g / m ² (dry state), followed by heating and drying, and further, aging treatment and the like to form a cured coating film according to the present invention. . In the above, as the above-mentioned resin composition, an ethylene-vinyl alcohol copolymer or the like was dissolved or kneaded, and further, since those films were cured, they were adjusted using an alcohol-water-based solution or the like. It is preferable to use a resin composition. 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.

In the above, specifically, the additive reacts with hydroxyl or the like of the ethylene-vinyl alcohol copolymer to form molecules of the ethylene-vinyl alcohol copolymer by chemical bonding with each other. A polyfunctional compound capable of forming a three-dimensional network structure (cured) polymer compound or the like can be used in combination, for example, an alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, or the like. Zirconium alkoxide compounds such as methoxyzirconium and tetraethoxyzirconium, and metal alkoxide compounds such as tetramethoxytitanium and tetraethoxytitanium titanium alkoxide compounds can be used. Further, in the present invention, as the additive, for example, a compound having a functional group that reacts with active hydrogen such as a —CH ＝ CH ₂ group, ＝ C ＝ O group, —C≡N group, epoxy group, ethyleneimine group, etc. , -OH group, -SH group, -COOH
Group, compound having active hydrogen, such as -NH ₂ group, and other,
A crosslinking agent comprising a compound having a halogen group, a salt, a chelate-forming group, or the like can be used. Specifically, for example, dialdehyde compounds, dicarboxylic acid compounds, diimide compounds, di- or polyhydric alcohol compounds, diamine compounds, bisepoxy compounds, bisethylene imine compounds, divinyl compounds, zirconium compounds, titanium chelate compounds, Others can be used.

Furthermore, in the present invention, a polymer having a good adhesion to a deposited thin film of an inorganic oxide, for example, an N-unsubstituted polyalkyleneimine such as polyethyleneimine;
Polyethyleneimine-based polymers such as N-alkyl-substituted polyalkyleneimines and N-acyl-substituted polyalkyleneimines; polycarbodiimide-based polymers such as polycarbodiimide; polyvinylpyrrolidone; polyalkylated vinylpyrrolidone; A polymer, a polyvinylpyrrolidone-based polymer such as a copolymer of vinylpyrrolidone and styrene, and the like can be used. Furthermore, in the present invention, when a hydroxyl group or the like of the ethylene-vinyl alcohol copolymer and the above-mentioned metal alkoxide compound, a cross-linking agent or the like reacts to form a cross-linked structure, for example, a curing catalyst or the like is added. can do. Examples of the above-mentioned curing catalyst include, for example, tertiary amines which are substantially insoluble in water and soluble in an organic solvent. N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, and as acids, for example, sulfuric acid, hydrochloric acid, mineral acids such as nitric acid,
Organic acids such as acetic acid and tartaric acid can be used. It is sufficient to add a small amount as the amount used.

In the present invention, the above-mentioned ethylene-vinyl alcohol copolymer is used as a main component of the vehicle, and if necessary, an additive is optionally added thereto to form an alcohol-water-based solvent and a diluent. A resin composition which is sufficiently kneaded is prepared by a method such as the above, coated by a usual coating method, and then heated and dried, and further subjected to an aging treatment or the like to thereby obtain a coating. A film can be formed. Thus, the above-mentioned coating film is excellent in close adhesion to a vapor-deposited thin film of an inorganic oxide, the bonding strength between the two is extremely strong, and no phenomenon such as peeling between the layers is observed. In the present invention, a barrier film composed of three layers, ie, two layers of a vapor-deposited thin film of an inorganic oxide and the above-mentioned coating film, is formed, thereby further improving the barrier properties against oxygen gas, water vapor gas and the like. And transparency,
It is excellent in heat resistance, hot water resistance, laminating suitability, etc., and can produce an extremely good laminated material.

Next, in the present invention, as the print pattern layer constituting the laminated material according to the present invention, for example, a usual gravure ink composition, offset ink composition, Using a letterpress ink composition, a screen ink composition, and other ink compositions, for example, a gravure printing method, an offset printing method,
Use letterpress printing method, silk screen printing method, other printing methods such as characters, figures, pictures, symbols,
It can be configured by forming a desired print pattern made of other materials. In the above, various ink compositions are, for example, one of the vehicles constituting the ink composition.
One or more kinds of coloring agents such as dyes and pigments are added thereto, and further, if necessary, for example, fillers, stabilizers, plasticizers, antioxidants Add optional additives such as light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc., and knead well with solvents, diluents, etc. It is possible to use ink compositions of various forms.

Next, in the present invention, as the heat-sealing resin forming the heat-sealing resin layer constituting the laminated material according to the present invention, for example, the heat-sealing resin is 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, as the above-mentioned laminated material, specifically, for example, films or sheets of various known resins
Or, for example, a film of cellophane or the like, synthetic paper, various paper substrates, and the like. 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 can be selected from a range of several μm to 300 μm. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

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
H has an extremely excellent effect of 1.0 cc / m ² · day · atm or less. 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 is used for packaging in various useful forms suitable for filling and packaging various articles by making a bag or a box using the laminated material. 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.

[0035]

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 vapor-deposited thin film was formed on the silicon oxide vapor-deposited thin film formed above by a reactive vacuum vapor deposition method using a heating method (EB). (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻³ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁵ mbar EB output: 40 KW Film transport speed: 600 m / Minutes (3). Next, a plasma treatment is performed on the aluminum oxide vapor-deposited thin film surface immediately after the formation of the aluminum oxide vapor-deposited thin film in the vapor deposition apparatus under the following conditions to form a plasma-treated surface on the aluminum oxide vapor-deposited thin film surface. did. (Plasma treatment conditions) Plasma treatment gas; helium gas and oxygen gas Degree of vacuum: 1.0 × 10 ⁻⁵ mbar (before gas introduction) 1.0 × 10 ⁻² mbar (after gas introduction) Gas ratio; helium gas: oxygen Gas = 2: 7 Plasma power: 3 kW Processing speed; 300 m / min (4). Next, using a gravure printing machine, a gravure coat roll was placed in the first color on the plasma-treated surface of the above-mentioned evaporated aluminum oxide thin film, and an ethylene-vinyl alcohol copolymer (ethylene A resin composition consisting of 100 parts by weight of a 15% solution of ion-exchanged water and n-propyl alcohol (1/1) solvent having a content of 32 mol%) was used for the gravure roll coating method. To form a coating film having a thickness of 1.1 g / m ² (dry state), followed by heat treatment at 120 ° C. for 5 minutes to form a cured coating film. Such a barrier film was produced. 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. (5). 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 base material, a biaxially stretched polypropylene film having a thickness of 20 μm (trade name, manufactured by Nimura Chemical Industry Co., Ltd., F
OK, one-sided corona-treated product) was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a deposited silicon oxide film having a thickness of 150 mm was formed on the above biaxially oriented polypropylene film under the following conditions. Formed on one side. (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, under the same conditions as the vapor deposition conditions described in (2) of Example 1 above, aluminum was used as a vapor deposition source, and an oxygen gas was supplied onto the silicon oxide vapor deposited thin film field. A 200- [mu] m-thick deposited aluminum oxide thin film was formed by a reactive vacuum deposition method using a heating (EB) heating method. (3). Next, the plasma-treated surface is formed on the deposited aluminum oxide thin film surface in the same manner as in the method described in (2) of Example 1 to form a plasma-treated surface. In the processing surface, the first embodiment
As in (4) above, use a gravure printing machine
A roll for gravure coating is placed on the color, and ethylene-vinyl alcohol copolymer (ethylene content 32 mol%)
Resin obtained by adding 20 parts by weight of a 5% solution of polyethyleneimine (manufactured by Nippon Shokubai Kagaku Co., Ltd.) to 100 parts by weight of a 15% solution of ion-exchanged water and n-propyl alcohol (1/1) solvent. The composition was coated by a gravure roll coating method to a thickness of 1.1 g / m2.
² (dry state) coating film is formed.
A coating film was formed by heat treatment at 20 ° 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, under the same conditions as the vapor deposition conditions described in (2) of Example 1 above, aluminum was used as a vapor deposition source, and an oxygen gas was supplied onto the silicon oxide vapor deposited thin film field. A 200- [mu] m-thick deposited aluminum oxide thin film was formed by a reactive vacuum deposition method using a heating (EB) heating method. (3). Next, the plasma-treated surface is formed on the deposited aluminum oxide thin film surface in the same manner as in the method described in (2) of Example 1 to form a plasma-treated surface. In the processing surface, the first embodiment
As in (4) above, use a gravure printing machine
A roll for gravure coating is placed on the color, and ethylene-vinyl alcohol copolymer (ethylene content 32 mol%)
10 parts by weight, 34 parts by weight of tetraethoxysilane, water 15
Aqueous resin composition consisting of 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of tertiary amine, and 3.4 parts by weight of epoxysilane was used, and this was coated by a gravure roll coating method. 1.1 g / m ² thickness
(Dry state) coating film is formed, and then
Heat treatment was performed at 0 ° C. for 1 minute 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 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 (5) of Example 1 described above, the thickness of the biaxially stretched polyethylene terephthalate film on which the print pattern layer was formed was formed 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 low-density polyethylene film having a thickness of 70 μm was extruded and laminated. Except for the above, a barrier film and a laminate according to the present invention were produced in exactly the same manner as in Example 1 above.

Example 5 In Example 1 (3), instead of the resin composition of Example 1 (3), an ion of an ethylene-vinyl alcohol copolymer (ethylene content 32 mol%) was used. Exchange water and n
A resin composition obtained by adding 1 part by weight of a 30% solution of zirconium acetate in the same solvent to 100 parts by weight of a 15% solution in propyl alcohol (1/1) solvent is used as a gravure alcohol. A coating film having a thickness of 1.1 g / m ² (dry state) was formed by a coating method, and then heat-treated at 120 ° C. for 1 minute.
Forming a hardened film, and otherwise the above Example 1
A barrier film and a laminate according to the present invention were produced in exactly the same manner as described above.

Example 6 In Example 1 (3), instead of the resin composition of Example 1 (3), an ion of an ethylene-vinyl alcohol copolymer (ethylene content 32 mol%) was used. Exchange water and n
Propyl alcohol (1/1) A resin composition obtained by adding 1 part by weight of a 30% solution of a carbodiimide in the same solvent to 100 parts by weight of a 15% solution in a solvent is used. Coating by a coating method to form a coating film having a thickness of 1.1 g / m ² (dry state), followed by heat treatment at 120 ° C. for 1 minute.
Forming a hardened film, and otherwise the above Example 3
A barrier film and a laminate according to the present invention were produced in exactly the same manner as described above.

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. Then, a coating cured film was formed on the vapor-deposited thin film of aluminum oxide in the same manner as in Example 1 to produce a barrier film. Next, a desired multicolor printed pattern layer is formed on the coating cured film of the barrier film in the same manner as in Example 1 above. An adhesive layer was formed. Furthermore,
In the same manner as in Example 1, a low-density polyethylene film having a thickness of 70 μm was laminated 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. Then, a coating cured film was formed on the vapor-deposited thin film of aluminum oxide in the same manner as in Example 1 to produce a barrier film. next,
On the coating cured film of the barrier film,
A desired multicolor print pattern layer was formed in the same manner as in Example 2 described above, and thereafter, a laminating adhesive layer was formed on the print pattern layer surface. Further, in the same manner as in Example 2 described above, a non-stretched polypropylene film having a thickness of 70 μm was laminated 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 silicon oxide vapor-deposited thin film was formed 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.
Then, a coating cured film was formed on the vapor-deposited thin film of aluminum oxide in the same manner as in Example 1 to produce a barrier film. Next, a desired multicolor printed pattern layer is formed on the coating cured film of the barrier film in the same manner as in Example 3 above, and then a laminating layer is formed on the printed pattern layer surface. An adhesive layer was formed. Further, in the same manner as in Example 3 described above,
m of unstretched polypropylene film was laminated to produce a laminated material.

Comparative Example 4 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and the 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 plasma-treated surface was formed on the vapor-deposited thin film of aluminum oxide in the same manner as in Example 1 to produce a barrier film. Next, a desired multicolor print pattern layer is formed on the plasma-treated surface of the barrier film in the same manner as in Example 1 above, and then the adhesive for laminating is formed on the print pattern layer surface. A layer was formed. Further, the first embodiment described above
Similarly, a low-density polyethylene film having a thickness of 70 μm was laminated to produce a laminated material.

Comparative Example 5 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 plasma-treated surface was formed on the vapor-deposited thin film of aluminum oxide in the same manner as in Example 1 to produce a barrier film. Next, a desired multicolor print pattern layer is formed on the plasma-treated surface of the barrier film in the same manner as in Example 2 described above, and then an adhesive for laminating is formed on the print pattern layer surface. A layer was formed. Further, in the same manner as in Example 2 described above,
m of unstretched polypropylene film was laminated to produce a laminated material.

COMPARATIVE EXAMPLE 6 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.
Then, a plasma-treated surface was formed on the above-described evaporated aluminum oxide thin film surface in the same manner as in Example 1 above.
A barrier film was manufactured. Next, a desired multicolor print pattern layer is formed on the plasma-treated surface of the barrier film in the same manner as in Example 3 described above, and thereafter, an adhesive for laminating is formed on the print pattern layer surface. A layer was formed. Furthermore,
In the same manner as in Example 3 described above, a non-stretched polypropylene film having a thickness of 70 μm was laminated to produce a laminated material.

Experimental Example 1 The following data was measured for each of the barrier films and the laminates produced in Examples 1 to 6 and Comparative Examples 1 to 6 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 Laminate Strength This was measured with a tensilon with a width of 15 mm after aging of the laminated material. (4). Measurement of surface free energy This is the vapor-deposited thin film surface of inorganic oxide of the barrier film,
The measurement was performed on the plasma-treated surface using a wetting reagent. The above measurement results are shown in Table 1 below. In Table 1, the unit of oxygen permeability is [cc / m ²
· Day · atm], the unit of water vapor permeability is [g / m ² · day · atm], and the unit of laminate strength is [gf / 15 mm width]. The unit of surface free energy is [dyne / c
m].

[0048]

[Table 1]

As is clear from the results shown in Table 1 above, the laminated materials according to Examples 1 to 6 have an oxygen permeability and a water vapor permeability of 1.0 cc / m ² · day · atm, 1.
It was 0 g / m ² · day · atm or less, and the laminate strength was good. In contrast, Comparative Examples 1 to 3
The laminated material according to (1) has an oxygen permeability and a water vapor permeability of 1.
0cc / m ² · day · atm, 1.0g / m ² · da
y · atm or less, but the laminate strength is remarkably inferior. Further, the laminates according to Comparative Examples 4 to 6 have good laminate strength, but have high oxygen permeability and water vapor. The transmittance was remarkably inferior. The above results show that the laminated materials according to Examples 1 to 6 can improve the laminating strength, the surface free energy and the like by the plasma treated surface, and provide a coating film. This indicates that the oxygen permeability and the water vapor permeability can be improved. In addition, the laminated materials according to Examples 1 to 6 show a phenomenon in which the laminated base material is broken and peeled off. However, the laminated materials according to Comparative Examples 1 to 3 are each a vapor-deposited inorganic oxide thin film and a coating film. And the laminates according to Comparative Examples 4 to 6 exhibited a phenomenon in which the laminated base material was broken and peeled off.

[0050]

As is apparent from the above description, the present invention focuses on modifying the surface of a vapor-deposited thin film of an inorganic oxide by a physical vapor deposition method. In addition, a vapor-deposited thin film of an inorganic oxide by a chemical vapor deposition method is provided, and further, a vapor-deposited thin film of an inorganic oxide by a physical vapor deposition method is provided on the vapor-deposited thin film of the inorganic oxide. On the vapor-deposited thin film surface of the oxide, oxygen, nitrogen, argon, or helium is provided with a plasma treatment surface with a gas composed of one or more kinds of helium.
A barrier film is manufactured by providing a coating film of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle, and the barrier film is replaced with another plastic film, or Paper base material, and other materials such as arbitrarily laminated to produce a laminated material,
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 articles to produce packaging products, improve the tight adhesion between the deposited thin film of inorganic oxide and the coating film, have excellent gas barrier properties against oxygen gas and water vapor, etc. Long-term stable distribution by preventing reforming, etc.,
It has storage suitability, etc., and is excellent in transparency, so that the contents can be visually recognized from the outside, and furthermore, it has excellent flexibility, heat resistance, laminate strength, etc. A useful barrier film capable of producing an excellent and excellent packaged product at low cost and a laminated 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 low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an inorganic oxide by a chemical vapor deposition method.

FIG. 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 Base film 3 Deposited thin film of inorganic oxide by chemical vapor deposition 4 Deposited thin film of inorganic oxide by physical vapor deposition 5 Plasma treated surface 6 Coating film 7 Printed picture layer 8 H Sealing resin layer

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) B32B 27/36 B32B 27/36 B65D 65/40 B65D 65/40 D Term (Reference) 3E086 AC07 AD01 AD02 BA04 BA14 BA15 BA24 BA40 BB02 BB04 BB22 BB41 BB51 CA01 CA11 CA28 CA35 4F100 AA17B AA17C AA19C AA20B AH02D AH06D AH08D AK01A AK01D AK01E AK06 AK07A AK42A AK48A AK51G AK69D AL05D BA04 BA05 BA07 BA10A BA10D BA44B CA02D CB02 EH66B EH66C EJ38A EJ60C EJ61C EJ67D GB16 GB23 GB66 HB31 JD02 JD03 JD04 JJ03 JK06E JK13 JL12E JM02B JM02C JN01 YY00B YY00D YY00E

Claims (12)

[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 substance, and a plasma-treated surface with a gas comprising one or more of oxygen, nitrogen, argon, or helium is provided on the surface of the vapor-deposited thin film of the inorganic oxide. A barrier film having a coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle on a treated surface. 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 method according to claim 1, wherein the inorganic oxide vapor-deposited thin film formed by physical vapor deposition comprises an inorganic oxide vapor-deposited thin film formed by vacuum vapor deposition. 6. The barrier film according to 6. 8. The method 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.
The barrier film described in 4, 5, 6 or 7. 9. The method according to claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%. The barrier film to be described. 10. The resin composition according to claim 1, wherein the resin composition contains at least one of a metal alkoxide compound, a cross-linking agent, a polymer having high adhesion to a vapor-deposited thin film of an inorganic oxide, and a silane coupling agent. Claims 1, 2, 3, 4, 5,
10. The barrier film described in 6, 7, 8 or 9. 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 thin film of oxygen, nitrogen, argon, or helium on the thin film surface of the inorganic oxide.
A plasma-treated surface with a gas comprising two or more species is provided, and a coating film made of a resin composition containing a saponified ethylene-vinyl acetate copolymer as a main component of a vehicle is further provided on the plasma-treated surface. A laminated material characterized in that at least a heat-sealing resin layer is provided on a surface of a coating film of a barrier film provided with (a). 12. A laminate having a laminating strength of at least 600 gf / 15 mm width between a coating film surface and a heat-sealing resin layer surface constituting a barrier film. A laminate according to claim 11.