JP2000127285A - Barrier film and laminate employing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film and a laminate, employing the same, which is improved in an air-tight bonding property between the deposited thin film of an inorganic oxide as well as gas barrier property with respect to oxygen gas, steam or the like and, further, prominent in transparency, heat resistant property, flexibility, laminating strength and the like. SOLUTION: An inorganic oxide deposited thin film 3, produced through physical gas phase epitaxial method, is provided on one side of a substrate film 2 while a plasma treated surface 4, treated by one kind or two kinds or more of oxygen, nitrogen, argon or helium, is provided on the inorganic oxide deposited thin film 3. Further, a barrier film 1, in which a coating film 5, produced by a resin composition containing ethylene vinyl alcohol copolymer as the principal constituent of the vehicle of the same, is provided on the plasma treated surface 4, and a laminate, employing the barrier film 1, can be 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 having a barrier property against oxygen gas and water vapor. Excellent, furthermore, transparency,
The present invention relates to a barrier film excellent in heat resistance, flexibility, laminating suitability and the like, and a laminated material using the same.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, 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, so-called gas barrier property. By the way, as a barrier material against oxygen gas or water vapor gas, various kinds of materials have been developed and proposed in the past.
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. Furthermore,
In the above-described vapor-deposited film, in order to further improve the function of blocking oxygen gas or water vapor gas, that is, the function of so-called gas barrier property, for example, ethylene-vinyl alcohol is deposited on the inorganic oxide vapor-deposited film. A barrier film such as a polymer or a polyvinylidene chloride resin is used, and a coating film or a film laminated film of the same is provided, and a coating film of an inorganic oxide deposited film and a barrier resin is used. A barrier material provided with a two-layer barrier layer including a film laminated film has also been proposed. 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 material certainly has an oxygen gas barrier property, a water vapor gas barrier property, etc., and further has a fragrance retention property, and is expected to have a certain effect. Although it can be done, it is a fact that it is still a material that cannot be said to be a satisfactory material. 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. It is possible to form a vapor-deposited film on any of the base films by a vacuum vapor-deposition method or the like with respect to the vapor-deposited film, but is it possible to improve the gas barrier properties against oxygen gas, water vapor gas, etc. Whether or not is related to the heat resistance of the base film. For example, when a heat-resistant base film such as a polyethylene terephthalate-based resin film is used as the base film, it is preferably used as the base film because it has heat resistance. It has the effect of improving the properties and the like. However, as the base film, for example, a biaxially stretched polypropylene film, a non-stretched polypropylene film, or, when using a base film having poor heat resistance such as a low-density polyethylene film, a vapor-deposited film by a vacuum vapor deposition method or the like. Although formation is technically possible, it is difficult to expect a significant improvement in barrier properties, and it cannot always be said that it is sufficiently satisfactory. Further, as the above-mentioned base film, for example, when a polyethylene terephthalate resin film is used, the polyethylene terephthalate resin film has rigidity and hardness, and further has wrinkles on the film. It is liable to occur, and therefore is not suitable for packaging materials requiring 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.

Furthermore, using a physical vapor deposition method (PVD method) such as the above-mentioned 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 chemical vapor deposition method, the vapor-deposited film of the inorganic oxide After forming
Further, a barrier resin such as an ethylene-vinyl alcohol copolymer is used on the inorganic oxide vapor-deposited film, and a coating film or a film laminate film is provided thereby to form a two-layer barrier. In the barrier material formed by forming a conductive film, the tight adhesion between the deposited film of the inorganic oxide and the coating film or the film laminated film made of the barrier resin is poor, the laminating aptitude is lacking, and It is a fact that a phenomenon occurs and it cannot be said that it is sufficiently satisfactory. 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. Then, first, on one surface of the substrate film, provided a vapor-deposited thin film of an inorganic oxide by physical vapor deposition, and further on the vapor-deposited thin film surface of the inorganic oxide, oxygen, nitrogen, argon, or,
Plasma treatment with a gas comprising one or more kinds of helium is performed to form a plasma treatment surface on the inorganic oxide vapor-deposited thin film surface, and further, an ethylene-vinyl alcohol copolymer is further provided on the plasma treatment surface. A barrier film is manufactured by providing a coating film of a resin composition containing as a main component of a vehicle, and the barrier film is made of another plastic film or a paper base material or other material. Arbitrarily laminated to produce a laminated material, 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, Various products such as pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. were filled and packaged to produce packaging products. The product showed excellent adhesion between the vapor-deposited inorganic oxide thin film and the coating film. And steam Against improve gas barrier properties, deterioration of the contents, stable long-term distribution to prevent modification or the like,
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. The present invention has been accomplished by finding a useful barrier film capable of producing extremely excellent and good packaging products at a low cost and a laminated material using the same.

That is, according to the present invention, an inorganic oxide vapor-deposited thin film is provided on one surface of a substrate film by a physical vapor deposition method, and oxygen, nitrogen, argon is deposited on the inorganic oxide vapor-deposited thin film surface. Or a plasma treatment surface with a gas comprising one or more of helium is provided.
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 laminate using the same. is there.

[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 an inorganic oxide by physical vapor deposition,
Further, a plasma-treated surface 4 of a gas comprising one or more of oxygen, nitrogen, argon, or helium is provided on the surface of the vapor-deposited thin film 3 of the inorganic oxide. The basic structure is that a coating film 5 made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle is provided. Next, as the laminated material 1a according to the present invention,
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. 1 if necessary, and the entire surface including the printing pattern layer 6 is further provided. In addition, the basic structure is that it has at least a heat-sealing resin layer 7. Note that FIG.
In the drawings, reference numerals 2, 3, 4, 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, 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 a physical vapor deposition method is shown in FIG. 3. FIG. 3 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 3, in a vacuum chamber 12 of a take-up type vacuum evaporation apparatus 11, a base film 2 unwound from an unwinding roll 13 is cooled through guide rolls 14 and 15 to a cooled core. -Guided to the singing drum 16; Thus, the evaporation source 1 heated by the crucible 17 is placed on the base film 2 guided on the cooled coating drum 16.
8. For example, metal aluminum or aluminum oxide is evaporated, and if necessary, oxygen gas or the like is blown out from the oxygen blow-out port 19 and supplied.
Through the masks 20, 20, for example, a vapor-deposited thin film of an inorganic oxide such as aluminum oxide is formed, and then, in the above, the base film 2 on which the vapor-deposited thin film of an inorganic oxide such as aluminum oxide is formed, , Guide roll 1
By feeding the film through 5 'and 14' and winding it up on a take-up roll 21, a deposited thin film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention.

In the above, as a thin film of an inorganic oxide deposited by physical vapor deposition, any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al) ), Magnesium (M
g), calcium (Ca), potassium (K), tin (S
n), sodium (Na), boron (B), titanium (T
A vapor-deposited thin film of an oxide of a metal such as i), lead (Pb), zirconium (Zr), or yttrium (Y) can be used. Thus, as materials suitable for packaging materials, etc.,
Examples include a vapor-deposited thin film of an oxide of a metal such as silicon (Si) and aluminum (Al). Thus, the above-mentioned vapor-deposited thin film of a metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and the notation is, for example, SiO _x , A
lO _X, MO _X (However, as such as MgO _X, in the formula, M
Represents a metal element, and the value of X has a different range depending on the metal element. ). Further, as the range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg).
Is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, Boron (B)
1, 5, 0 for titanium (Ti), 0 for lead (Pb)
-1, zirconium (Zr) can take a value of 0-2, and yttrium (Y) can take a value of 0-1.5.
In the above, when X = 0, it is a perfect metal, it is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention,
As a packaging material, generally, there are few examples of use except for silicon (Si) and aluminum (Al). Silicon (Si) is 1.0 to 2.0, aluminum (Al)
Can be used in the range of 0.5 to 1.5. In the present invention, the thickness of the thin film of the inorganic oxide as described above varies depending on the type of the metal or the metal oxide to be used.
It is desirable to arbitrarily select and form it within the range of 100 to 1000 °. 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 furthermore, a barrier film composed of two layers of a 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-mentioned 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, a method of generating plasma in the plasma processing includes, for example, a DC glow discharge and a high frequency (Audio Frequency).
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, as a main component of a vehicle, an ethylene-vinyl alcohol copolymer which constitutes a barrier film or a laminate material according to the present invention will be described. Then, as such a coating film, for example, one or more of ethylene-vinyl alcohol copolymers as a main component of the vehicle, and further, if necessary, for example, a filler, a stabilizer, Optionally add additives such as plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc., and solvents and diluents. A resin composition composed of a solvent type, an aqueous type, or an emulsion type, etc., which is sufficiently kneaded by using, for example, a roll coating method, a gravure method, and the like. Coating method such as coating method, kiss roll coating method, squeeze roll coating method, reverse roll coating method, curtain flow coating method, etc. Amount, for example, 0.1 g / m ² to
About 10 g / m ² (dry state), preferably 0.5 g / m ²
forming a coating film according to the present invention by coating so as to have an m ^{2 to 5} g / m ² (dry state) and then subjecting to heat drying and further aging treatment. Can be. In the above, as the resin composition, an ethylene-vinyl alcohol copolymer or the like is dissolved or kneaded, and further, these are cured, so that the resin composition adjusted using an alcohol-water-based solution or the like is used. It is preferable to use an alcohol component such as n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, ethyl alcohol. , Methyl alcohol, etc., and in the above-mentioned alcohol-water solution, the mixing ratio of alcohol to water is, for example, alcohol-water.
It is desirable to adjust the alcohol-water solution by mixing 50 to 70 parts by weight of water with 50 to 30 parts by weight of water.

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 the 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, 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.

Next, in the present invention, a silane coupling agent having binary reactivity can be added. Examples of the silane coupling agent include, for example, 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- One or more of aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-aminopropylsilicone can be used. As the amount of use, only a small amount may be added. 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 the acids, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and 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 two layers of a vapor-deposited thin film of an inorganic oxide and the above-described coating film is formed, thereby further improving the barrier properties against oxygen gas, water vapor gas, and the like, and It is excellent in transparency, heat resistance, hot water resistance, laminating suitability, etc., and can produce an extremely good laminated material.

Next, in the present invention, as a print pattern layer constituting the laminate according to the present invention, for example, a usual gravure ink composition, offset ink composition, Using an ink composition such as a relief printing ink composition, a screen ink composition, etc., for example, a gravure printing method, an offset printing method,
Use letterpress printing method, silk screen printing method, other printing methods such as characters, figures, pictures, symbols,
It can be configured by forming a desired print pattern made of other materials. In the above, various ink compositions 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, 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-mentioned various conditions is arbitrarily selected and used, and these are arbitrarily laminated together with the material constituting the above-described laminated material according to the present invention to form a desired laminated material. can do. In the above, specifically, for example, films or sheets of various resins, films of cellophane or the like, synthetic paper, paper base materials, and the like can also 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,
It can be used by selecting from a range of several μm to about 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 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, the effect is 1.0 cc / m ² · day · atm or less. The above-described measurement of the oxygen permeability is carried out by the aforementioned method, for example, MOCON (MOCO, USA).
23 ° C., 90% using an oxygen permeability measuring instrument (model name, OX-TRAN 2/20) manufactured by N)
It can be measured under RH conditions.

The laminated material according to the present invention produced as described above can be used for packaging in various useful forms suitable for filling and packaging various articles by 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). A 12 μm-thick biaxially stretched polyethylene terephthalate film was used as a base material, which was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then the film was fed out onto a coating drum. The biaxially stretched polyethylene terephthalate was prepared by an oxidation reaction vacuum evaporation method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as an evaporation source.
An aluminum oxide deposited thin film having a thickness of 200 ° was formed on the thin film. (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 / Min Deposition surface: Corona treated surface (2). 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 (3). 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. (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 base material, a biaxially stretched polypropylene film having a thickness of 20 μm (trade name, manufactured by Nimura Chemical Industry Co., Ltd., F
OK, single-sided corona-treated product) and vapor-depositing aluminum oxide having a thickness of 200 ° on the biaxially stretched polypropylene film in the same manner as described in (1) and (2) of Example 1 above. A thin film was formed, and a plasma-treated surface was formed on the aluminum oxide deposited thin film surface. (2). 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 For a 100% by weight of a 15% solution of ion-exchanged water and n-propyl alcohol (1/1) solvent having a content of 32 mol%, a 5% solution of polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd.) was added. The resin composition was added by weight and coated by a gravure roll coating method to form a coating film having a thickness of 1.1 g / m ² (dry state). For 5 minutes to form a cured coating film, thereby producing a barrier film according to the present invention. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. (3). Next, the biaxially stretched 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). Using a biaxially stretched nylon film having a thickness of 15 μm as a substrate, a film thickness is formed on the biaxially stretched nylon film in the same manner as described in (1) and (2) of Example 1 above. A 200 ° aluminum oxide deposited thin film is formed, and the aluminum oxide deposited thin film
A plasma treated surface was formed. (2). 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 Content 32 mol%) 1
An aqueous resin composition comprising 0 parts by weight, 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst, and 3.4 parts by weight of epoxysilane. This was coated by a gravure roll coating method and had a thickness of 0.9 g / m2.
² (dry state) coating film is formed.
A coating cured film was formed by heat treatment at 20 ° C. for 1 minute 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. (3). Next, the biaxially stretched nylon film having the printed picture layer formed thereon is mounted on a first delivery roll of a dry laminating machine, and 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 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 5 minutes.
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. 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 5 minutes.
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.

Comparative Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a substrate, and one surface of the biaxially stretched polyethylene terephthalate film was used in the same manner as in Example 1 above. Then, a thin film of aluminum oxide is formed on the thin film of aluminum oxide. Then, a gravure coating roll is placed on the first color of the thin film of aluminum oxide using a gravure printing machine. A 15% solution of propylene copolymer (ethylene content 32 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent
A resin composition consisting of 100 parts by weight 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);
Heat treatment was performed at 120 ° C. for 5 minutes to form a coating cured film, thereby producing a barrier film. Next, in the same manner as in Example 1 above, using the gravure printing machine described above, a gravure ink composition was applied onto the coating cured film of the barrier film to obtain a desired coating composition. A printed pattern layer of a color was formed, and further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, a low-density polyethylene film having a thickness of 70 μm is prepared, one surface of which is subjected to corona discharge treatment, and the surface of the adhesive layer for laminating the biaxially stretched polyethylene terephthalate film on the corona discharge treated surface. Were opposed to each other, and both were laminated by a dry lamination method to produce a laminated material.

Comparative Example 2 A biaxially oriented polypropylene film having a thickness of 20 μm was used as a substrate, and aluminum oxide was deposited on one surface of the biaxially oriented polypropylene film in exactly the same manner as in Example 1 above. A thin film is formed, and then a gravure coating roll is placed on the first color of the aluminum oxide vapor-deposited thin film using a gravure printing machine, and the same resin composition as in Comparative Example 1 is used. Use a gravure
1.1 g / m thickness by coating
² (dry state) coating film is formed.
Heat treatment was performed at 20 ° 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, subsequently, using the gravure printing machine described above, using a gravure ink composition, to form a desired multicolor print pattern layer, Further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, a non-stretched polypropylene film having a thickness of 70 μm 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.

Comparative Example 3 A biaxially stretched nylon film having a thickness of 20 μm was used as a substrate, and aluminum oxide was deposited on one surface of the biaxially stretched nylon film in exactly the same manner as in Example 1 above. A thin film is formed, and then a gravure printing roll is placed on the first color of the aluminum oxide vapor-deposited thin film using a gravure printing machine, and an ethylene-vinyl alcohol copolymer ( A resin composition consisting of 100 parts by weight of a 15% solution of ion-exchanged water having an ethylene content of 29 mol%) and n-propyl alcohol (1/1) solvent was used, and this was obtained by a gravure roll coating method. Coating was performed to form a coating film having a thickness of 1.1 g / m ² (dry state), and then heat-treated at 120 ° C. for 5 minutes.
A hardened film was formed to produce a barrier film. Next, a desired multicolor printed pattern layer was formed on the coating cured film of the barrier film by using the gravure ink composition using the gravure printing machine described above. Further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, a non-stretched polypropylene film having a thickness of 70 μm is prepared, one surface of which is subjected to a corona discharge treatment, and the laminating adhesive layer surface of the biaxially stretched nylon 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 4 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a substrate, and one surface of the biaxially stretched polyethylene terephthalate film was used in the same manner as in Example 1 above. Then, a vapor-deposited thin film of aluminum oxide was formed, and plasma-treated on the vapor-deposited thin film surface of the aluminum oxide to form a plasma-treated surface, thereby producing a barrier film. Next, on the plasma-treated surface of the barrier film, using a gravure printing machine, using a gravure ink composition in the same manner as in Example 1 above, to form a desired multicolor print pattern layer, Further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, thickness 70
A low-density polyethylene film having a thickness of μm was prepared, and one surface thereof was subjected to a corona discharge treatment, and the laminating adhesive layer surface of the biaxially stretched polyethylene terephthalate film was opposed to the corona discharge treatment surface, Both were laminated by dry lamination 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 aluminum oxide was deposited on one surface of the biaxially oriented polypropylene film in exactly the same manner as in Example 1 described above. A thin film was formed, and then a plasma-treated surface was formed on the vapor-deposited thin film of aluminum oxide to form a plasma-treated surface, thereby producing a barrier film. next,
On the plasma-treated surface of the barrier film, a gravure printing machine was used, a gravure ink composition was used, and a desired multicolor print pattern layer was formed in the same manner as in Example 1; An adhesive layer for laminating was formed on the surface of the printed picture layer. On the other hand, a non-stretched polypropylene film having a thickness of 70 μm is prepared, one surface of which is subjected to a corona discharge treatment, and the laminating adhesive layer surface of the biaxially stretched polypropylene film is opposed to the corona discharge treated surface. And both were laminated by a dry lamination method to produce a laminated material.

Comparative Example 6 A biaxially stretched nylon film having a thickness of 20 μm was used as a substrate, and aluminum oxide was deposited on one surface of the biaxially stretched nylon film in exactly the same manner as in Example 1 above. A thin film was formed, and then a plasma-treated surface was formed on the vapor-deposited thin film of aluminum oxide to form a plasma-treated surface, thereby producing a barrier film. Next, a desired multicolor printed picture layer was formed on the plasma-treated surface of the barrier film using a gravure ink composition using a gravure printing machine in the same manner as in Example 1 above. Further, an adhesive layer for laminating was formed on the surface of the printed pattern layer. On the other hand, a non-stretched polypropylene film having a thickness of 70 μm is prepared, one surface of which is subjected to a corona discharge treatment, and the laminating adhesive layer surface of the biaxially stretched nylon film is opposed to the corona discharge treated surface. And both were laminated by a dry lamination method to produce a laminated material.

EXPERIMENTAL EXAMPLE 1 The following data were measured for each of the barrier films and the laminates produced in Examples 1 to 6 and Comparative Examples 1 to 6 described 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 for a laminated material after aging, with a width of 15 mm using a tensilon (tensile speed 50 mm / mi).
n). (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].

[0045]

[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 extremely poor, and the laminates according to Comparative Examples 4 to 6 have good laminate strength, but have high oxygen permeability and water vapor permeability. The degree was remarkably inferior. From the above results, it is shown 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 treatment. This indicates that the oxygen permeability and the water vapor permeability can be improved. Examples 1 to 6
Shows a phenomenon in which the laminated base material is broken and peels off, but the laminates according to Comparative Examples 1 to 3 delaminate between the deposited thin film of inorganic oxide and the coating film. In addition, the laminated materials according to Comparative Examples 4 to 6 exhibited a phenomenon in which the laminated base material was broken and peeled off.

[0047]

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 is provided by physical vapor deposition, and furthermore, oxygen, nitrogen,
Plasma treatment is performed with a gas comprising one or more of argon and helium to form a plasma treatment surface on the inorganic oxide vapor-deposited thin film surface, and further, ethylene-vinyl alcohol is applied to the plasma treatment surface. A barrier film is manufactured by providing a coating film made of a resin composition containing a copolymer as a main component of a vehicle, and the barrier film is then replaced with another plastic film or a paper base material. A laminated material is produced by arbitrarily laminating other materials and the like, and then using the laminated material, producing a packaging container by bag making or box making, for example, in the packaging container, , Food and beverages, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc.
Excellent adhesion between the deposited thin film of inorganic oxide and the coating film, improved gas barrier properties against oxygen gas and water vapor, etc. It has distribution, storage suitability, etc., and is also excellent in transparency, so that the contents can be visually recognized from the outside,
Further, a useful barrier film which is excellent in flexibility, heat resistance, laminate strength, etc., does not have bag breakage, etc. and can produce extremely excellent and excellent packaging products at low cost, and a laminated material using the same. It can be manufactured.

[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 roll-up vacuum deposition apparatus showing an outline of a method of forming a vapor-deposited inorganic oxide thin film by physical vapor deposition.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Barrier film 2 Base film 3 Vapor-deposited thin film of inorganic oxide by physical vapor deposition method 4 Plasma treated surface 5 Coating film 6 Printing picture layer 7 Heat-sealing resin layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/36 B32B 27/36 B65D 65/40 B65D 65/40 DF term (Reference) 3E086 AC07 AD01 AD02 BA04 BA14 BA15 BA24 BA40 BB01 BB15 BB21 BB41 BB51 CA01 CA11 CA28 CA35 4F100 AA17B AA19B AH02C AH06C AH08C AK01A AK01C AK01D AK06 AK07A AK42A AK48A AK51G AK69C AL05C BA03 BA04 BA07 BA10A BA10C BA10D CA02C CB02 EH66B EJ38A EJ60B EJ61B EJ67C GB16 GB23 GB66 HB31 JA20B JD02 JD03 JD04 JJ03 JK06C JK13 JL11C JL12D JM02B JN01 YY00B YY00C

Claims (12)

[Claims] An inorganic oxide vapor-deposited thin film is formed on one surface of a base film by physical vapor deposition, and oxygen, nitrogen, argon, or helium is further deposited on the inorganic oxide vapor-deposited thin film. And a coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle. A barrier film provided. 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 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. 4. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film formed by physical vapor deposition comprises an aluminum oxide vapor-deposited thin film formed by vacuum vapor deposition.
2. The barrier film described in 1. 5. The surface free energy of a plasma processing surface
Is 45 dyne / cm or more, the barrier film according to claim 1, 2, 3, or 5, wherein 6. The barrier film according to claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%. 7. The method according to claim 1, wherein the resin composition contains a metal alkoxide compound.
7. The barrier film according to 5 or 6. 8. The barrier film according to claim 1, wherein the resin composition contains a crosslinking agent. 9. The resin composition according to claim 1, wherein the resin composition contains a polymer having high adhesion to a vapor-deposited thin film of an inorganic oxide. 8. The barrier film according to 8. 10. The method according to claim 1, wherein the resin composition contains a silane coupling agent.
The barrier film described in 5, 7, 8, 9 or 10. 11. An inorganic oxide vapor-deposited thin film formed by physical vapor deposition on one surface of a substrate film, and oxygen, nitrogen, argon, or helium is further deposited on the inorganic oxide vapor-deposited thin film. And a coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle. A laminated material characterized in that at least a heat-sealing resin layer is provided on the surface of the coating film of the provided barrier film. 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.