JP2002166486A - Barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film useful to manufacture various types of packaging container having excellent barrier properties for preventing a permeation of an oxygen gas, steam or the like, by preventing occurrence of a crack or the like in a vapor-deposited film of an inorganic oxide such as a silicon oxide, an aluminum oxide or the like for constituting a transparent barrier film as a barrier material, excellent preservability, storage properties or the like by preventing a change of properties or the like of a content with a highly laminating strength. SOLUTION: The barrier film comprises the vapor-deposited film of the inorganic oxide provided on one surface of a base film, a primer agent layer of a composition containing a polyethyleneimine and provided on the vapor- deposited film of the inorganic oxide, and further a heat adhesive resin layer provided on the primer agent layer.

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 more particularly, to a barrier film which has excellent barrier properties for preventing permeation of oxygen gas, water vapor, etc., prevents deterioration of contents, and has extremely high laminating strength. The present invention relates to a barrier film useful for producing various packaging containers having excellent storage stability, storage stability and the like.

[0002]

2. Description of the Related Art Conventionally, packaging containers of various forms have been developed and proposed for filling and packaging foods and beverages, pharmaceuticals, chemicals, and the like. Usually, in order to prevent the deterioration of the contents, and further enhance the storage stability, storage properties, etc., as a material constituting the packaging container, a barrier material in various forms together with a plastic film or the like is used. It is used. Recently, as one of the barrier materials, one side of a base film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film is coated with an inorganic oxide such as silicon oxide or aluminum oxide. Attention has been paid to a transparent barrier film provided with a deposited film of an object, and packaging containers of various forms using this as a barrier material have been developed and proposed. This is a barrier material made of a plastic film such as a conventional polyvinylidene chloride-based resin or polyvinyl alcohol-based resin,
Alternatively, in comparison with a barrier material or the like made of a metal layer such as a resin film provided with an aluminum foil or a vapor-deposited film thereof, a barrier property of preventing permeation of oxygen gas, water vapor, or the like, a barrier equal to or higher than them In addition to having the function of water, it has excellent suitability for disposal as container garbage and the like. For example, even if it is disposed of as it is by incineration, it does not cause environmental destruction. The use, demand, and the like of the barrier material constituting the material are greatly expected in the future.

[0003]

However, as a barrier material, silicon oxide or aluminum oxide is applied to one surface of a base film such as the above biaxially stretched polyethylene terephthalate film or biaxially stretched nylon film. In a transparent barrier film provided with a deposited film of an inorganic oxide such as, silicon oxide constituting the transparent barrier film, a deposited film of an inorganic oxide such as aluminum oxide,
Since it is a glassy, inflexible thin film and a thin film that is extremely inflexible, cracks and the like can be easily formed on the inorganic oxide deposited film by the action of, for example, heat or pressure. There is a problem that occurs, once,
If cracks or the like occur in a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide, the barrier property of preventing the permeation of oxygen gas, water vapor, or the like is remarkably lacking, and there is a disadvantage that it cannot be used anymore. For example, a low-density polyethylene resin or the like is used on the surface of a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide which constitutes the above-mentioned transparent barrier film via an anchor coat agent layer or the like. Heating this to about 330 ° C. and laminating the melt-extruded resin layers while melt-extruding from an extruder or the like, the inorganic oxides such as silicon oxide and aluminum oxide are heated by the heating temperature of the above-mentioned melt-extruded resin layers. Cracks and the like are easily generated in the deposited film, and the barrier property of preventing permeation of oxygen gas, water vapor and the like is remarkably deteriorated. Further, a desired printed pattern layer is provided on the surface of the deposited film of an inorganic oxide such as silicon oxide or aluminum oxide constituting the transparent barrier film, and a heat-sealing resin layer or the like is further laminated. In the same manner as above, a laminated material is manufactured, and a bag is formed using the material, and various packaging containers are manufactured. Cracks and the like are easily generated, and there is a problem that the barrier property for preventing permeation of oxygen gas, water vapor and the like is remarkably lacking. In the transparent barrier film, the deposited film of the inorganic oxide such as silicon oxide and aluminum oxide constituting the transparent barrier film is vitreous, and the surface thereof is an extremely inert surface. Because of its remarkably lacking wettability, even if a heat-sealing resin layer is provided on the surface thereof, it lacks the laminating strength between the layers, and produces various desirable packaging containers. There is also a problem that it is difficult. Therefore, the present invention prevents the generation of cracks and the like in a deposited film of an inorganic oxide such as silicon oxide and aluminum oxide that constitutes a transparent barrier film as a barrier material, thereby preventing the transmission of oxygen gas, water vapor, and the like. Barrier film that has excellent barrier properties, prevents deterioration of contents, has extremely high laminating strength, and is useful for producing various types of packaging containers having excellent storage and storage properties. It is to be.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has provided an inorganic oxide vapor-deposited film on one surface of a base film, On the oxide deposited film, provided a primer agent layer consisting of a coating film of a composition containing polyethyleneimine,
Furthermore, on the primer agent layer, for example, a barrier film was produced by providing a heat-adhesive resin layer comprising a resin layer of a copolymer with ethylene-unsaturated carboxylic acid or its esterified product, Excellent barrier properties to prevent cracks and the like from being generated in the deposited film of inorganic oxides such as silicon oxide and aluminum oxide constituting the barrier layer and to prevent permeation of oxygen gas, water vapor and the like. Excellent lamination strength between the deposited film of the inorganic oxide and the heat-adhesive resin layer laminated through the layers, for example, the barrier film is overlapped with the surface of the heat-adhesive resin layer facing, Thereafter, the three peripheral edges are heat-sealed to produce a packaging bag, and then a sealed package is prepared by filling and packing the contents in the packaging bag.
The present invention has been completed by finding that a packaged product which avoids defective contents, liquid leakage and the like, prevents deterioration of the contents and the like, and is excellent in storability and storability can be manufactured.

That is, according to the present invention, an inorganic oxide vapor-deposited film is provided on one surface of a substrate film, and a primer containing a composition containing polyethyleneimine is further provided on the inorganic oxide vapor-deposited film. The present invention relates to a barrier film comprising a layer and a heat-adhesive resin layer provided on the primer agent layer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. First, the barrier film according to the present invention will be described with reference to the drawings by exemplifying one example of the layer structure thereof. FIGS. 1 and 2 show the layer structure of the barrier film according to the present invention. It is a schematic sectional drawing which shows.

First, in the present invention, as a barrier film A according to the present invention, as shown in FIG. 1, a vapor-deposited film 2 of an inorganic oxide is provided on one surface of a base film 1.
Further, a primer agent layer 3 made of a composition containing polyethyleneimine is provided on the inorganic oxide vapor-deposited film 2, and a heat-adhesive resin layer 4 is further formed on the primer agent layer 3. The basic structure is a structure in which the layers are sequentially stacked. As a specific example of the barrier film according to the present invention, as shown in FIG. A primer agent layer 3 composed of a coating film 3a made of a composition containing polyethyleneimine is provided on the film 2, and further, on the primer agent layer 3, for example, ethylene-unsaturated carboxylic acid or mention may be made of a barrier film a ₁ formed by laminating a heat-adhesive resin layer 4 made of a resin layer 4a by a copolymer of ester thereof sequentially. The above examples are examples of the barrier film according to the present invention, and the present invention is not limited thereto. For example, in the present invention, although not shown, as a deposited film of the inorganic oxide,
Not only a single layer film composed of one layer of the inorganic oxide vapor-deposited film but also a multilayer film or a composite film composed of two or more layers of the same or different inorganic oxide vapor-deposited films may be used. As a film, its purpose of use,
Depending on the contents to be filled and packed, their distribution channels, applications, etc.
Furthermore, it is possible to design and manufacture barrier films of various forms by arbitrarily laminating other base materials.

Next, in the present invention, the material constituting the barrier film according to the present invention, the manufacturing method thereof, etc. will be described. First, as the base film constituting the barrier film, an inorganic oxide is deposited thereon. Since a film is provided, a resin film or sheet having excellent properties in mechanical, physical, chemical, etc., and particularly having strength and toughness and having heat resistance is provided. Can be used. Specifically, in the present invention, examples of the base film include polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin,
Polycarbonate resin, polyethylene terephthalate
Polyester resins such as polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins,
Films or sheets of various resins such as polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, acetal resin, cellulose resin and others can be used. In the present invention, it is particularly preferable to use a film or sheet of a polypropylene resin, a polyester resin, or a polyamide resin.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, the cast molding method, the T-die method, and the cutting method are used. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, or a multi-layer coextrusion film forming using two or more kinds of resins. A film or a sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 100 μm.
And more preferably about 9 to 50 μm.

[0010] One or more of the above-mentioned various resins are used, and when the film is formed, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability,
For the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc., various plastic additives and additives can be added. Can,
The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
Antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, anti-blocking agents, coloring agents such as dyes and pigments, and the like can be used. Can also be used.

In the present invention, if necessary, the surface of the various resin films or sheets described above may be provided on the surface thereof in order to improve the tight adhesion with an inorganic oxide deposited film described later. A desired surface treatment layer can be provided in advance. In the present invention, as the surface treatment layer, for example, a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical or the like, Pretreatment such as others can be arbitrarily performed, and for example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above surface pretreatment is carried out as a method for improving the tight adhesion between a film or sheet of various resins and a deposited film of an inorganic oxide described later. As other methods for improving the film quality, for example, various resin films or sheets
A primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or
A surface treatment layer may be formed by arbitrarily forming a deposition anchor coating agent layer and the like. Examples of the coating agent layer in the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing a polyolefin resin such as polyethylene or polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

Next, in the present invention, the vapor-deposited inorganic oxide film constituting the barrier film according to the present invention will be described. As the vapor-deposited film of the inorganic oxide, for example, a chemical vapor deposition method, It can be manufactured by forming a single-layer film composed of one layer of an inorganic oxide vapor-deposited film or a multilayer film or a composite film composed of two or more layers by physical vapor deposition or a combination of both. It is.

In the present invention, the vapor-deposited inorganic oxide film formed by the above-mentioned chemical vapor deposition method will be further described.
For example, plasma chemical vapor deposition, thermal chemical vapor deposition,
Chemical vapor deposition such as photochemical vapor deposition (Chemica
l Vapor Deposition method, CVD method)
A deposited film of an inorganic oxide can be formed by using such a 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 an inert gas such as an argon gas or a helium gas is used as a carrier gas. Further, a vapor-deposited film of an inorganic oxide such as silicon oxide can be formed by using a low-temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. . In the above description, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. In order to
It is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method of forming a deposited film of an inorganic oxide by the above-described low-temperature plasma chemical vapor deposition method will be described. FIG. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a deposited oxide film. As shown in FIG. 3 described above, in the present invention, the vacuum chamber of the plasma enhanced chemical vapor deposition apparatus 21 is used.
The base film 1 is fed out from an unwinding roll 23 disposed in the inside 22, and the base film 1 is further transferred to an auxiliary roll.
The cooling / electrode drum 25 is conveyed onto the peripheral surface of the cooling / electrode drum 25 at a predetermined speed via the tool 24. Thus, in the present invention, a monomer for vapor deposition of an oxygen gas, an inert gas, an organic silicon compound or the like is supplied from the gas supply devices 26 and 27 and the raw material volatile supply device 28 and the like.
While supplying a gas, etc., and adjusting the mixed gas composition for vapor deposition comprising the same, the mixed gas composition for vapor deposition is introduced into the vacuum chamber 22 through the raw material supply nozzle 29, and the above cooling / cooling is performed. The glow discharge plasma 30 is placed on the substrate film 1 conveyed on the peripheral surface of the electrode drum 25.
To generate plasma and irradiate it to form a deposited film of an inorganic oxide such as silicon oxide. In the present invention, at this time, a predetermined electric power is applied to the cooling / electrode drum 25 from the power supply 31 arranged outside the vacuum chamber 22. The arrangement of the magnet 32 promotes the generation of plasma. Next, the base film 1 on which the vapor-deposited film of the inorganic oxide such as silicon oxide is formed is wound up on a winding roll 34 via an auxiliary roll 33, and the plasma chemical vapor phase according to the present invention is obtained. An inorganic oxide deposited film can be formed by a growth method. In the figure, 35
Represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, as a deposited film of the inorganic oxide,
Not only one layer of the deposited film of the inorganic oxide but also a multilayer film in which two or more layers are laminated may be used, and the material to be used may be used in one kind or in a mixture of two or more kinds. It is also possible to form a deposited film of an inorganic oxide mixed with materials.

In the above, the inside of the vacuum chamber 22 is
The pressure is reduced by the empty pump 35 and the degree of vacuum is 1 × 10^-1~ 1 × 1
0^-8Torr level, preferably vacuum degree 1 × 10^-3~ 1 ×
10 ^-7It is desirable to adjust to the Torr position.
You. In addition, in the raw material volatile supply device 28,
And the gas supply devices 26 and 27
Mixed with oxygen gas, inert gas, etc. supplied from
Vacuum gas through the raw material supply nozzle 29
−22. In this case, the mixed gas
The content of the organic silicon compound in the
Content is about 10-70%, inert gas content
Can be in the range of about 10-60%, for example,
The mixing ratio of organic silicon compound, oxygen gas and inert gas
The ratio can be about 1: 6: 5 to 1:17:14.
On the other hand, the cooling / electrode drum 25
Since the voltage is applied, the source in the vacuum chamber 22 is
Between the opening of the material supply nozzle 29 and the cooling / electrode drum 25
Glow discharge plasma 30 is generated in the vicinity, and this glow discharge plasma 30 is generated.
The discharge plasma 30 is formed of one or more gas components in a mixed gas.
Minutes, and in this state, the substrate
The film 4 is transported at a constant speed, and the glow discharge plasma
30, the substrate material on the peripheral surface of the cooling / electrode drum 25
A deposited film of an inorganic oxide such as silicon oxide is formed on the room 1
Is what you can do. At this time,
The degree of vacuum in the chamber is 1 × 10^-1~ 1 × 10^-FourTor
r position, preferably vacuum degree 1 × 10^-1~ 1 × 10^-2To
It is desirable to prepare at the rr position, and the base film
The transport speed of 4 is about 10 to 300 m / min, preferably,
It is desirable to adjust to 50-150m / min.
is there.

The above-mentioned plasma chemical vapor deposition apparatus 2
In 1, the formation of the deposited film of an inorganic oxide such as silicon oxide, on the substrate film 1, since it is formed into a thin film in the form of SiO _X while the plasma raw material gas is oxidized with oxygen gas, The formed deposited film of an inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible. The property is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness. Further, in the present invention, Si
O _X plasma by the substrate film 1 of the surface, is cleaned, the surface of the substrate film 1, a polar group and pretend - since radicals such as occurs, vapor deposited film of an inorganic oxide such as silicon oxide is formed and This has the advantage that the close adhesion with the base film 1 is high. Further, as described above, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is:
1 × 10 ^-1 to 1 × 10 ^-4 Torr, preferably 1 × 10 ^-1 Torr
Since the pressure is adjusted to about 10 ^-1 to 1 × 10 ^-2 Torr, the degree of vacuum for forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method is 1 × 10 ^-4 to 1 × 10 Torr. ^-5 Tor
Since the degree of vacuum is lower than that of the r-position, it is possible to shorten the time for setting the vacuum state when exchanging the base film 1 and to stabilize the degree of vacuum and stabilize the film forming process. is there.

In the present invention, a deposited silicon oxide film formed by using a vaporized monomer gas such as an organic silicon compound is chemically reacted with a vaporized monomer gas such as an organic silicon compound and oxygen gas. the reaction product is closely deposited on one surface of a substrate film, dense, and forms 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), and is a continuous thin film mainly composed of silicon oxide. Thus, from the viewpoints of transparency, barrier properties, etc., the silicon oxide deposited film of the general formula Si
O _X (provided that, X represents represents. A number of 1.3 to 1.9) is intended is preferably a thin film mainly composed of vapor-deposited film of silicon oxide represented by. In the above, the value of X changes depending on the molar ratio of the vaporized monomer gas to oxygen gas, the energy of the plasma, and the like. In general, the gas permeability decreases as the value of X decreases, but the film itself does Is yellowish,
Transparency worsens.

The silicon oxide deposited film is mainly composed of silicon oxide, and further contains at least one compound of one or more of carbon, hydrogen, silicon and oxygen. It is characterized by comprising a deposited film containing the kind by a chemical bond or the like. For example,
When the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained due to chemical bonding or the like. To give a specific example, CH
Hydrocarbon with _three sites, SiH ₃ silyl, Si
Examples thereof include hydrosilica such as H ₂ silylene and hydroxyl derivative such as SiH ₂ OH silanol. In addition to the above, the type, amount, and the like of the compound contained in the deposited silicon oxide film can be changed by changing the conditions and the like of the deposition process. Thus, the content of the above compound in the deposited silicon oxide film is 0.1 to 5%.
About 0%, preferably about 5 to 20% is desirable. In the above, if the content is less than 0.1%,
Impact resistance, spreadability, flexibility, etc. of the deposited film of silicon oxide become insufficient, and due to bending, scratches, cracks, etc. are easily generated, and it becomes difficult to stably maintain high barrier properties, On the other hand, if it exceeds 50%, the barrier properties are undesirably reduced. Furthermore, in the present invention, the content of the above compound in the silicon oxide vapor deposition film is preferably reduced in the depth direction from the surface of the silicon oxide vapor deposition film, whereby the silicon oxide vapor deposition film is formed. On the surface of the above, the impact resistance and the like can be enhanced by the above-mentioned compounds and the like, while at the interface with the base film, the content of the above-mentioned compounds is small, so that the base film and the deposited film of silicon oxide Has the advantage that the tight adhesion of the polymer becomes strong.

Thus, in the present invention, the above-mentioned deposited film of silicon oxide may be, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec.)
onion Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide film using a method of performing analysis by ion etching in the depth direction or the like using a surface analysis device such as O.I. can do. In the present invention, the thickness of the deposited silicon oxide film is preferably about 50 to 4000 °, and specifically, about 100 to 1000 °. Then, in the above, 1000 °, furthermore, 40
When the thickness is more than 00 °, cracks and the like are easily generated in the film, which is not preferable.
If it is less than 0 °, it is not preferable because it is difficult to exhibit the effect of the barrier property. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited film of silicon oxide, 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.

Next, in the above, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, 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 handling properties and a formed continuous film. It is a particularly preferable raw material in view of its properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

Next, in the present invention, the inorganic oxide deposited film formed by the above-mentioned physical vapor deposition method will be described in more detail. Method, sputtering method,
Physical vapor deposition methods such as an ion plating method and an ion cluster beam method (Physical VaporDe)
A deposition film of an inorganic oxide can be formed using a position method or a PVD method). In the present invention, specifically, a metal oxide is used as a raw material, which is heated and vaporized, and this is vapor-deposited on one side of a base film, or a metal or a metal oxide is used as a raw material. Oxidation reaction deposition method of using a substance, introducing oxygen, oxidizing and depositing on one of the base film, and plasma-assisted oxidation reaction deposition method of promoting the oxidation reaction by plasma, etc. Can be formed. In the above, as a heating method of the evaporation material, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), or the like can be used.

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 structural diagram showing an example of a roll-up type vacuum evaporation apparatus. It is. As shown in FIG. 4, in the vacuum chamber 42 of the take-up type vacuum evaporation apparatus 41, the base film 1 unwound from the unwinding roll 43 is cooled through guide rolls 44 and 45 and cooled. -Guided to the singing drum 46; Thus, on the substrate film 1 guided on the cooled coating drum 46,
The evaporation source 48 heated in the crucible 47, for example, metal aluminum or aluminum oxide is evaporated,
Further, if necessary, oxygen gas or the like is spouted from the oxygen gas outlet 49 and, while supplying the gas, a deposited film of an inorganic oxide such as aluminum oxide is formed through the masks 50 and 50, Next, in the above, for example, the base film 1 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through guide rolls 45 'and 44' and wound up on a take-up roll 51. In addition, a deposited film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention. In the present invention, first, using the above-mentioned winding type vacuum evaporation apparatus, the first
Forming a layer of inorganic oxide on the layer, and then forming a layer of inorganic oxide on the layer of inorganic oxide, Forming an inorganic oxide vapor deposition film consisting of two or more multilayer films by connecting these in series using a vacuum evaporation system and forming an inorganic oxide vapor deposition film continuously. Can be.

In the above, as the inorganic oxide deposited film, basically any thin film obtained by depositing a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg) , Calcium (C
a), potassium (K), tin (Sn), sodium (N
a), a vapor-deposited film of an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. Thus, preferred are silicon (Si), aluminum (A
1) and the like.
And Thus, deposited films of oxides of the above metals, silicon oxides, aluminum oxides, can be referred to as a metal oxide like such as magnesium oxide, the notation is, for example, SiO _X, AlO _X MO such as MgO _X
X (where M represents a metal element, and the value of X is
The range differs depending on the metal element. ). The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0 to 1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
Can take a value in the range of 0 to 2 and yttrium (Y) can take a value in the range of 0 to 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 end of the range of X is a fully oxidized value. In the present invention, generally, except for silicon (Si) and aluminum (Al), examples used are scarce. Silicon (Si) is 1.0 to 2.0, aluminum (A)
For l), a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the above-mentioned inorganic oxide vapor-deposited film varies depending on the type of metal or metal oxide to be used.
It is desirable to arbitrarily select and form it within the range of about 00 °, preferably about 100 to 1000 °. Further, in the present invention, as the deposited metal film of the inorganic oxide, the metal to be used, or as the oxide of the metal, used in one kind or a mixture of two or more kinds, and the inorganic oxide mixed with different materials is used. A vapor deposition film can also be formed.

In the present invention, the inorganic oxide deposited film constituting the liquid paper container and the like according to the present invention is
For example, a composite film composed of two or more vapor-deposited films of different types of inorganic oxides can be formed and used by using both physical vapor deposition and chemical vapor deposition. Thus, as a composite film composed of two or more layers of the above-mentioned vapor-deposited films of different types of inorganic oxides, first, a dense, flexible material is formed on a base film by a chemical vapor deposition method. A deposited film of an inorganic oxide capable of preventing the occurrence of cracks is provided, and then a deposited film of an inorganic oxide formed by physical vapor deposition is provided on the deposited film of the inorganic oxide to form two or more layers. It is desirable to form an inorganic oxide deposited film composed of a composite film composed of: Of course, in the present invention, contrary to the above, an inorganic oxide vapor-deposited film is first provided on the base film by a physical vapor deposition method, and then densely deposited by a chemical vapor deposition method. In addition, it is also possible to provide a deposited film of an inorganic oxide which is rich in flexibility and can relatively prevent the occurrence of cracks, thereby forming a deposited film of an inorganic oxide composed of a composite film composed of two or more layers. is there.

Next, in the present invention, the primer agent layer constituting the barrier film according to the present invention will be described.
If necessary, add additives such as a stabilizer, a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber, and the like as needed, and add a solvent, a diluent, and the like, and sufficiently mix. To prepare an aqueous composition. Alternatively, in the present invention,
Polyethyleneimine is the main component of the vehicle, and the silane coupling agent is about 0.05 to 10% by weight, preferably about 0.1% to 5% by weight, and the filler is 0 to 1 to 30% by weight of the polyethyleneimine. 0.1-20% by weight, preferably about 1-10% by weight, and further, if necessary, a stabilizer, a curing agent, a crosslinking agent, a lubricant, an ultraviolet absorber,
An aqueous composition is prepared by arbitrarily adding other additives, adding a solvent, a diluent, and the like, and mixing well. Thus, the composition prepared above is used and is used, for example, in roll coat, gravure coat, knife coat, dip coat.
Coating on the inorganic oxide vapor-deposited film provided on one side of the above-mentioned base film by a coating method, a spray coating method or another coating method, and then drying the coated film. Then, the solvent, diluent and the like are removed, and if necessary, aging treatment or the like is performed to form the primer agent layer according to the present invention. In the present invention, the thickness of the primer agent layer is, for example, 0.1
^{g / m 2 ~5.0g / m 2} ( dry state) position is desirable.
Thus, in the present invention, the above-described primer agent layer improves the tight adhesion between the inorganic oxide vapor-deposited film and the heat-adhesive resin layer and the like, and also increases the elongation of the primer agent layer. It improves the post-processing suitability such as laminating or box-forming, and prevents the occurrence of cracks and the like in the deposited film of the inorganic oxide during the post-processing.

In the above, as the polyethyleneimine constituting the above-mentioned composition, for example, a perfect linear polymer having a complete linear height represented by the following formula synthesized by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst: Not a numerator, 1
A high molecular compound having a branched structure including secondary, secondary and tertiary amines can be used. (In the above formula, x and y represent positive numbers.) As the polyethyleneimine, specifically, Nippon Shokubai Co., Ltd., trade name, Epomin (registered trademark) and the like can be used. it can. Thus, in the present invention, the use of polyethyleneimine as described above improves the tight adhesion between the inorganic oxide vapor-deposited film and the heat-adhesive resin layer and the like, and also increases the elongation of the primer agent layer. To improve the post-processing suitability such as laminating or box-forming, and to prevent the occurrence of cracks and the like in the inorganic oxide deposited film during the post-processing.

Next, in the above, as the silane coupling agent constituting the above-mentioned composition, an organic functional silane monomer having dual reactivity can be used.
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-aminopropylmethyldimethoxysilane, γ
One or more of aqueous solutions of -ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-aminopropylsilicone can be used.

In the silane coupling agent as described above, a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group or the like is hydrolyzed to form a silanol group (SiOH). , A metal constituting the deposited film of the inorganic oxide, or an active group on the surface of the deposited film of the inorganic oxide, for example, by any action with a functional group such as a hydroxyl group, for example, causing a reaction such as a dehydration condensation reaction. The silane coupling agent is modified by a covalent bond or the like on the surface of the deposited inorganic oxide film, and a strong bond is formed on the surface of the deposited inorganic oxide film of the silanol group itself by adsorption or hydrogen bonding. . On the other hand, the other end of the silane coupling agent vinyl, methacryloxy, amino, epoxy, or
Organic functional groups such as mercapto are formed on the thin film of the silane coupling agent, for example, a heat-adhesive resin layer,
It reacts with the substances constituting other layers to form a strong bond, and further, the other base materials and the like are firmly and tightly adhered to each other via the above-mentioned heat-adhesive resin layer and the like, and the laminates are formed. Increase strength,
Thus, in the present invention, a strong laminated structure having high laminate strength can be formed. In the present invention, by utilizing the inorganic and organic properties of the silane coupling agent, through a layer such as a vapor-deposited film of an inorganic oxide and a heat-adhesive resin layer, and the like, a close contact with another substrate or the like is made. The adhesiveness is improved, thereby significantly increasing the laminating strength and the like.

Next, in the present invention, as the filler constituting the above composition, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like are used. be able to. Thus, the above-mentioned filler adjusts the viscosity and the like of the above-mentioned composition liquid, improves its coating suitability, and combines with polyethyleneimine via a silane coupling agent to form a coating film. It is to improve power.

In the present invention, if necessary, the above composition may be, for example, a polyurethane resin, a polyester resin, a polyamide resin, an epoxy resin, a phenol resin, a (meth) acrylic resin. A composition is prepared by arbitrarily adding one or more of a resin such as a polyvinyl acetate resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, and others. Is what you can do.

Next, in the present invention, the heat-adhesive resin layer constituting the barrier film according to the present invention will be described. As the heat-adhesive resin layer, an ethylene-unsaturated carboxylic acid or an ester thereof is used. Can be used. Specifically, a melt-extruded resin layer melt-extruded at 310 ° C. or lower by a copolymer with ethylene-unsaturated carboxylic acid or its esterified product can be used. Can be. More specifically, for example, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-maleic acid copolymer And one or more copolymers with an ethylene-unsaturated carboxylic acid or an ester thereof, etc., and heated to, for example, 310 ° C. or lower, preferably about 280 ° C. to 300 ° C. Then, a melt-extruded resin layer melt-extruded can be used. In the above-mentioned copolymer, it is preferable that the unsaturated carboxylic acid or the esterified product constituting the copolymer is contained in the range of 5 to 30 mol% and copolymerized.

In the present invention, the heat-adhesive resin layer is usually formed of a resin which can be melted by heat and fused to each other, specifically, a low-density polyethylene or a linear (linear) low-temperature resin. Using a high-density polyethylene or the like, a heat-adhesive resin layer can be formed with the melt-extruded resin layer while heating and melt-extruding the same. In this case, a low-density polyethylene or a linear (Linear) Low-density polyethylene must be heated to about 330 ° C. to 350 ° C. and melt-extruded. For this reason, a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide constituting a barrier film. In this case, a heating temperature of about 330 ° C. to 350 ° C. acts, and cracks and the like are easily generated in a deposited film of an inorganic oxide such as silicon oxide and aluminum oxide. In which it would not significantly degrade the barrier properties to prevent. Therefore, in the present invention,
Focusing on a copolymer with an ethylene-unsaturated carboxylic acid or an esterified product thereof, which can be melt-extruded and laminated at a lower temperature, the temperature is adjusted to 310 ° C. or lower, preferably 280 ° C. or lower.
It is laminated through a melt-extruded resin layer that is heated to about 300 ° C. and melt-extruded. Furthermore, in the present invention, the barrier film is formed by using a resin layer melt-extruded at a temperature of 310 ° C. or lower, preferably 300 ° C. or lower by a copolymer with an ethylene-unsaturated carboxylic acid or an esterified product thereof. Anchor on the surface of the primer agent layer
It can be melt-extruded and laminated without using a coating agent layer or the like, that is, a no-anchor coating agent layer.

In the present invention, as the heat-adhesive resin layer, for example, an extruder or the like is used, and one or two or more of the above-mentioned copolymer resins are used as a single layer. Alternatively, the resin composition may be melt-extruded into multiple layers to form a melt-extruded resin layer or the like, and a heat-adhesive resin layer may be provided. In the present invention, the thickness of the heat-adhesive resin layer is about 10 μm to 200 μm, preferably about 20 μm.
About 80 μm is desirable.

In the present invention, other materials forming the barrier film according to the present invention include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear Low-density polyethylene, polypropylene, ethylene-propylene copolymer and other resin films or sheets, or polyvinylidene chloride-based resins having a barrier property against oxygen, water vapor, etc., polyvinyl alcohol-based resins, ethylene -A film or sheet of a resin such as a vinyl alcohol copolymer, an MXD polyamide-based resin, or a polynaphthalene terephthalate-based resin; Use various colored resin films or sheets that have a light-shielding property and are formed into films. It is possible. These materials are
One or more can be used in combination. The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, and furthermore,
A thickness of about 10 μm to 100 μm is desirable.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. A material that satisfies the above conditions can be arbitrarily selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
Any known resin film or sheet such as a diene resin, a polyacetal resin, a polyurethane resin, nitrocellulose, or the like can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to about 300 μm. Further, in the present invention, as the film or sheet, extrusion film formation,
Any film such as an inflation film or a coating film may be used. In addition, for example, films such as cellophane, various paper base materials, synthetic paper, and the like can also be used.

Next, in the present invention, the material constituting the barrier film according to the present invention can form a desired printed pattern layer on any of the materials.
As the print pattern layer, for example, on the above material, a normal gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, using other ink compositions, For example, using a gravure printing method, an offset printing method, a letterpress printing method, a silk screen printing method, and other printing methods, for example, a character, a figure, a pattern, a symbol, and the like are formed by forming a desired printing pattern consisting of others. can do. In the above ink composition, the vehicle constituting the ink composition includes, for example, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer,
Polystyrene resin, styrene-butadiene copolymer,
Vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting resin Cellulose resins such as poly (meth) acrylic resin, melamine resin, urea resin, polyurethane resin, phenolic resin, xylene resin, maleic resin, nitrocellulose, ethylcellulose, acetylbutylcellulose, and ethyloxyethylcellulose Use a mixture of one or more of rubber resins such as chlorinated rubber and cyclized rubber, petroleum resins, natural resins such as rosin and casein, oils and fats such as linseed oil and soybean oil, and other resins. be able to. In the present invention, one or more kinds of the above-mentioned vehicles are used as a main component, and one or more kinds of coloring agents such as dyes and pigments are added thereto.
Optionally add fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, and other additives. ,solvent,
Ink compositions of various forms which are sufficiently kneaded with a diluent or the like can be used.

In the present invention, a method for producing a barrier film using the above-mentioned materials will be described. As the method, a method for laminating a usual packaging material, for example, a wet laminating method is used. Law,
Dry lamination method, solventless dry lamination method, extrusion lamination method, T-die extrusion molding method, co-extrusion lamination method, inflation method, co-extrusion inflation method, etc. it can. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a pretreatment such as a corona treatment, a plasma treatment, an ozone treatment, or the like can be optionally performed. -Anchoring agents such as polyurethane (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy,
Laminates such as polyvinyl acetate, cellulose and others
A known anchor coating agent such as an adhesive for lamination, an adhesive for laminating and the like can be arbitrarily used.

In the present invention, the method for producing the barrier film according to the present invention will be specifically described.
For example, it can be performed by a dry lamination method of laminating through a laminating adhesive layer with a laminating adhesive, or an extrusion laminating method of laminating through a melt extruded resin layer of a melt extruded adhesive resin. In the above, as the laminating adhesive, for example, one-component or two-component curing or non-curing type vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, etc. Adhesives for lamination such as solvent-based, water-based, and emulsion-based adhesives, and rubber-based adhesives and the like can be used. As a coating method of the laminating adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method, or another method can be used. The coating amount is preferably 0.1 to 10 g
/ M ² (dry state), more preferably 1 to 5 g / m ^2
2 (dry state). The laminating adhesive may optionally include an adhesion promoter such as a silane coupling agent.

In the above, as the melt-extruded adhesive resin, for example, a heat-sealing resin which can be melted by heat and can be fused to each other can be used. High density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene polymerized using metallocene catalyst
α-olefin copolymer, polypropylene, ethylene-
Vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer , Methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, modified with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Resins such as polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin and others can be used. The thickness of the melt-extruded resin layer of the melt-extruded adhesive resin is preferably about 5 to 100 μm, more preferably,
It is about 10 to 50 μm. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the above-described lamination, an adhesive improving agent such as an anchor coat agent may be coated. Examples of the anchor coating agent include, for example, organic titanium-based anchor coating agents such as alkyl titanates, isocyanate-based anchor coating agents,
Polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, and various other aqueous or oil-based anchor coating agents can be used. In the present invention, the anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods,
The solvent, diluent and the like can be dried to form an anchor coat agent layer. The coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

Next, in the present invention, a method of producing a bag or a box using the barrier film according to the present invention to manufacture a packaging container will be described. Are prepared, and the heat-bonded resin layer, which is the innermost layer, is superposed with the surfaces facing each other, and then the outer peripheral edge is heat-sealed on three sides. A three-way seal type flexible packaging container can be manufactured by forming a sealing portion and providing an opening above. Thus, in the present invention, contents such as food and drink, etc. are filled from the opening of the three-way seal type flexible packaging container produced above, and then the upper opening is filled. -Sealing to form an upper sealing portion and the like, and further, if necessary, for example, boil processing,
By performing retort treatment and the like, it is possible to manufacture packaged products of various forms. Furthermore, in the present invention, the barrier film according to the present invention is used, and the surface of the inner layer is folded and opposed, or the two sheets are overlapped, and further, the peripheral edge of the outer periphery is, for example, Side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seal type), pleated seal Heat seals such as heat seals, flat bottom seals, square bottom seals, etc.
To manufacture various types of packaging containers according to the present invention. In addition, for example, a self-supporting packaging bag (standing pouch) can be manufactured,
Further, in the present invention, a tube container or the like can be manufactured by using the above laminated material. In the above, as the heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like is used. Can be done in a way. In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container containing a paper base as the packaging container, for example, a laminated material in which a paper base or the like is laminated on the barrier film according to the present invention is manufactured.
Next, a blank plate for manufacturing a desired paper container is manufactured from this, and thereafter, the body, bottom, head and the like are formed using the blank plate, for example, a brick type, a flat type or a glass type. A bell-top type liquid paper container or the like can be manufactured. Moreover, the shape can be manufactured by any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

In the present invention, the packaging container manufactured as described above can be used for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and various other products such as others. It is used for filling and packaging of articles. Thus, in the present invention, particularly, for example, soy sauce,
Liquid foods or drinks such as liquid sachets for filling and packaging sours, soups, etc., soft packaging bags for filling and packaging raw confectionery, etc., or soft packaging bags for filling and packaging boiling or retort foods, etc. The present invention is useful as a packaging container for filling and packaging foods and the like containing.

[0043]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Then, under the following conditions, the above biaxially stretched polyethylene terephthalate film was used. On the corona-treated surface of the film, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 3.0: 3.0 (unit: slm) Degree of vacuum in vacuum chamber; 6 × 10 ⁻⁶ mBar Degree of vacuum in the deposition chamber; 2 to 5 × 10 ⁻³ mBar Cooling / electrode drum supply power; 10 kW Line speed; 100 m / min Immediately after the formation, a glow-discharge plasma generator was used to apply a power of 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 ( Unit: slm) is used, and the mixed gas pressure is 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more. (2). Next, a polyethyleneimine-based primer coating agent (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine-based coating agent, trade name, Epomin P1000) was used on the plasma-treated surface formed in (1) above. This Gurabiaro - Turkey - by method, a film thickness 0.1 g / m ² (dry)
And then dried to form a primer agent layer. (3). Next, using an extrusion laminating machine, an ethylene-methacrylic acid copolymer (trade name, Nucrel N0908C, manufactured by Mitsui DuPont Polychemicals Co., Ltd., : 280 ° C,
(Extruded film thickness: 30 μm), and extruded by laminating to form a heat-adhesive resin layer composed of a melt-extruded resin layer.
Thereafter, an aging treatment was performed at 40 ° C. for 3 days to produce a barrier film according to the present invention. (4). Next, 2 of the barrier film produced above
A sheet is prepared, and the surfaces of the heat-adhesive resin layer are overlapped so as to face each other.
A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured. The liquid sachet packaging product manufactured above is
It was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., withstanding distribution in the market, and excellent in storage and preservation.

Example 2 (1) A 15 μm-thick biaxially stretched nylon film was used as a base material, and this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and oxidized to a thickness of 150 ° under the following conditions. An evaporated silicon film was formed on one surface of the 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 Degree of vacuum in evaporation chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface A plasma-treated surface was formed on the surface of the deposited silicon oxide film in the same manner as in Example 1 above. (2). Next, a polyethyleneimine-based primer coating agent (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine-based coating agent, trade name, Epomin P1000) was used on the plasma-treated surface formed in (1) above. This Gurabiaro - Turkey - by method, a film thickness 0.1 g / m ² (dry)
And then dried to form a primer agent layer. (3). Next, using an extrusion laminating machine, an ethylene-methacrylic acid copolymer (trade name, Nucrel N0908C, manufactured by Mitsui DuPont Polychemicals Co., Ltd., : 280 ° C,
(Extruded film thickness: 30 μm), and extruded by laminating to form a heat-adhesive resin layer composed of a melt-extruded resin layer.
Thereafter, an aging treatment was performed at 40 ° C. for 3 days to produce a barrier film according to the present invention. (4). Next, 2 of the barrier film produced above
A sheet is prepared, and the surfaces of the heat-adhesive resin layer are overlapped so as to face each other.
A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured. The liquid sachet packaging product manufactured above is
It was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., withstanding distribution in the market, and excellent in storage and preservation.

Embodiment 3 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
The above biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then unwound. Was used as a vapor deposition source, and while supplying oxygen gas, a 200-Å-thick aluminum oxide vapor-deposited film was formed by a vacuum vapor deposition method using an electron beam (EB) heating method under the following vapor deposition conditions. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface : Corona-treated surface Next, immediately after forming the above-mentioned aluminum oxide vapor-deposited film having a thickness of 200 °, a plasma-treated surface was formed on the aluminum oxide-deposited film surface in the same manner as in Example 1 described above. (2). Next, a polyethyleneimine-based primer coating agent (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine-based coating agent, trade name, Epomin P1000) was used on the plasma-treated surface formed in (1) above. This Gurabiaro - Turkey - by method, a film thickness 0.1 g / m ² (dry)
And then dried to form a primer agent layer. (3). Next, using an extrusion laminating machine, an ethylene-methacrylic acid copolymer (trade name, Nucrel N0908C, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., extrusion temperature: (280 ° C., extruded film thickness 30 μm), and extruded by lamination to form a heat-adhesive resin layer composed of a melt-extruded resin layer.
Thereafter, an aging treatment was performed at 40 ° C. for 3 days to produce a barrier film according to the present invention. (4). Next, 2 of the barrier film produced above
A sheet is prepared, and the surfaces of the heat-adhesive resin layer are overlapped so as to face each other.
A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured. The liquid sachet packaging product manufactured above is
It was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., withstanding distribution in the market, and excellent in storage and preservation.

Example 4 (1) A 15 μm-thick biaxially stretched nylon film was used as a base material, and this was mounted on a delivery roll of a take-up type vacuum evaporation apparatus. Using an aluminum as a vapor deposition source and supplying oxygen gas, an oxidation reaction vacuum vapor deposition method using an electron beam (EB) heating method is used to deposit a 200 ° -thick aluminum oxide film on the biaxially stretched nylon film. A deposited film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 1.0 × 10 ⁻⁶ mbar EB output: 40 kW Film transport speed: 500 m / min Next, a plasma-treated surface was formed in the same manner as in Example 1 on the aluminum oxide-deposited film surface of the biaxially stretched nylon film on which the aluminum oxide-deposited film was formed. (2). Next, a polyethyleneimine-based primer coating agent (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine-based coating agent, trade name, Epomin P1000) was used on the plasma-treated surface formed in (1) above. This Gurabiaro - Turkey - by method, a film thickness 0.1 g / m ² (dry)
And then dried to form a primer agent layer. (3). Next, using an extrusion laminating machine, an ethylene-methacrylic acid copolymer (trade name, Nucrel N0908C, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., extrusion temperature: (280 ° C., extruded film thickness 30 μm), and extruded by lamination to form a heat-adhesive resin layer composed of a melt-extruded resin layer.
Thereafter, an aging treatment was performed at 40 ° C. for 3 days to produce a barrier film according to the present invention. (4). On the other hand, a paper substrate [Potlatch, USA
tch), a corona discharge treatment is applied to one surface of a basis weight of 425 g / m ² ], a low-density polyethylene resin is used for the corona discharge treatment surface, and this is extrusion-coated to obtain a thick film. A low-density polyethylene resin layer having a thickness of 30 μm was formed.
Next, using an extrusion laminating machine, a polyethyleneimine-based anchor coating agent layer was provided on the non-coated surface of the paper base, and then the surface of the anchor coating agent layer was formed. The thickness 12 constituting the barrier film produced in (3) above
The surface of a biaxially stretched polyethylene terephthalate film of μm is opposed, and an ethylene-methacrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemical Co., Ltd., product surface, Nucrel N0908C, extrusion temperature: 290 ° C., extruded film) This was subjected to extrusion lamination, and the above-mentioned paper base material and the barrier film were bonded together to produce a laminate according to the present invention. (5). Then, using the laminated material produced above,
In accordance with the shape of the bell-top type liquid paper container, a fold rule is engraved vertically or horizontally or diagonally and punched to produce a blank plate having a margin for glue,
The end face of the blank plate manufactured as described above is subjected to a skive hemming treatment to prevent permeation of the contents and liquid leakage, etc., and then the end face treatment is performed. The heat-adhesive resin layer in the margin portion is melted, the other end of the blank plate is overlapped on the melted surface, and the two are stuck together to form a body-sealed seal portion, thereby forming a cylindrical slip. -Was manufactured. Next, the cylindrical thread manufactured as described above is used.
The inner surface of the bottom of the tube is roasted by hot air, the heat-adhesive resin layer on the inner surface is melted, and a press seal is performed to form a bottom seal portion. After filling the inside, the inner surface of the top is burned with hot air, the heat-adhesive resin layer on the inner surface is melted, press-sealed to form a gable-top seal portion, and the contents are filled and packaged. The sealed liquid paper container according to the present invention was manufactured. The sealed liquid paper container produced above does not show any occurrence of roasting pinholes, etc., and furthermore has excellent barrier properties against oxygen gas, water vapor, etc., and also has excellent fragrance retention, and its contents are not deteriorated. It was not recognized, was excellent in laminate strength, etc., endured distribution in the market, and was excellent in storage and preservation.

Comparative Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Then, under the following conditions, the above biaxially stretched polyethylene terephthalate film was used. On the corona-treated surface of the film, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 3.0: 3.0 (unit: slm) Degree of vacuum in vacuum chamber; 6 × 10 ⁻⁶ mBar Degree of vacuum in the deposition chamber; 2 to 5 × 10 ⁻³ mBar Cooling / electrode drum supply power; 10 kW Line speed; 100 m / min Immediately after the formation, a glow-discharge plasma generator was used to apply a power of 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 ( Unit: slm) is used, and the mixed gas pressure is 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more. (2). Next, using an extrusion laminating machine, an ethylene-methacrylic acid copolymer (trade name: Nucrel N0908C, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., extrusion temperature: 280) was applied to the surface of the plasma-treated surface formed as described above. C., extruded film thickness of 30 μm), and extruded by lamination to form a heat-adhesive resin layer composed of a melt-extruded resin layer.
Thereafter, aging treatment was performed at 40 ° C. for 3 days to produce a barrier film. (3). Next, 2 of the barrier film produced above
A sheet is prepared, and the surfaces of the heat-adhesive resin layer are overlapped so as to face each other.
A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

Comparative Example 2 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
The above biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then unwound. Was used as a vapor deposition source, and while supplying oxygen gas, a 200-Å-thick aluminum oxide vapor-deposited film was formed by a vacuum vapor deposition method using an electron beam (EB) heating method under the following vapor deposition conditions. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface : Corona-treated surface Next, immediately after forming the above-described aluminum oxide vapor-deposited film having a thickness of 200 °, a plasma-treated surface was formed on the aluminum oxide-deposited film surface in the same manner as in Reference Example 1 described above. (2). Next, using an extrusion laminating machine, an ethylene-methacrylic acid copolymer (trade name: Nucrel N0908C, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., extrusion temperature: 280) was applied to the surface of the plasma-treated surface formed as described above. C., extruded film thickness of 30 μm), and extruded by lamination to form a heat-adhesive resin layer composed of a melt-extruded resin layer.
Thereafter, aging treatment was performed at 40 ° C. for 3 days to produce a barrier film. (3). Next, 2 of the barrier film produced above
A sheet is prepared, and the surfaces of the heat-adhesive resin layer are overlapped so as to face each other.
A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

Comparative Example 3 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Then, under the following conditions, the above biaxially stretched polyethylene terephthalate film was used. On the corona-treated surface of the film, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 3.0: 3.0 (unit: slm) Degree of vacuum in vacuum chamber; 6 × 10 ⁻⁶ mBar Degree of vacuum in the deposition chamber; 2 to 5 × 10 ⁻³ mBar Cooling / electrode drum supply power; 10 kW Line speed; 100 m / min Immediately after the formation, a glow-discharge plasma generator was used to apply a power of 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 ( Unit: slm) is used, and the mixed gas pressure is 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more. (2). Next, a polyethyleneimine-based primer coating agent (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine-based coating agent, trade name, Epomin P1000) was used on the plasma-treated surface formed in (1) above. This Gurabiaro - Turkey - by method, a film thickness 0.1 g / m ² (dry)
And then dried to form a primer agent layer. (3). Next, using an extrusion laminating machine, a low density polyethylene (trade name, Mirason 16P, manufactured by Mitsui Chemicals, Inc., extrusion temperature:
(330 ° C., extruded film thickness: 30 μm), and extruded by laminating to form a heat-adhesive resin layer composed of a melt-extruded resin layer. To produce a barrier film. (4). Next, 2 of the barrier film produced above
A sheet is prepared, and the surfaces of the heat-adhesive resin layer are overlapped so as to face each other.
A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

Experimental Examples The barrier films produced in Examples 1 to 4 and Comparative Examples 1 to 3 were measured for oxygen permeability and laminate strength. (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 Laminate Strength This was performed by measuring a sample with a Tensilon tester (Model: STA-1150, manufactured by Orientec Co., Ltd.).
The film was cut to a width of mm, and the peel strength was measured so as to form a T-shaped peel at the peel interface. The test results are shown in Table 1 below.

[0051] In Table 1 above, the unit of oxygen permeability is [cc / m
² / day · 23 ° C. · 90% RH], and the unit of the laminating strength is [kg / 15 mm].

As is evident from the test results shown in Table 1 above, those according to Examples 1 to 4 were excellent in oxygen permeability, laminate strength and the like. In contrast, Comparative Example 1,
Sample No. 2 was inferior in oxygen permeability, laminating strength and the like, and Sample No. 3 was inferior in oxygen permeability.

[0053]

As apparent from the above description, the present invention provides an inorganic oxide vapor-deposited film on one surface of a substrate film, and further comprises a polyethylene film on the inorganic oxide vapor-deposited film. A primer agent layer comprising a coating film of a composition containing imine is provided, and a resin such as an ethylene-unsaturated carboxylic acid or a copolymer thereof with an esterified product thereof is formed on the primer agent layer. A barrier film is manufactured by providing a heat-adhesive resin layer composed of a layer, and a barrier film is formed by preventing a crack or the like from being generated in a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide. It has excellent barrier properties to prevent the permeation of gas, water vapor, etc., and also has excellent laminating strength between the inorganic oxide deposited film and the heat-adhesive resin layer laminated via the primer agent layer. Sex fill Are laminated with the surfaces of the heat-adhesive resin layer facing each other, and then the three peripheral edges are heat-sealed to produce a packaging bag. By manufacturing a sealed package in which a product is filled and packed, it is possible to avoid poor sealing, liquid leakage, etc., prevent deterioration of the contents, etc., and manufacture a packaged product having excellent storage stability and storage properties. That you can do it.

[Brief description of the drawings]

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

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

FIG. 3 is a schematic configuration diagram showing an outline of a plasma enhanced chemical vapor deposition apparatus.

FIG. 4 is a schematic configuration diagram showing an outline of a take-up type vacuum evaporation apparatus.

[Explanation of symbols]

A, A ₁ Barrier film 1 Base film 2 Deposited film of inorganic oxide 3, 3a Primer layer 4, 4a Thermal adhesive resin layer

Continued on the front page F-term (reference) 4F100 AA00B AA19B AA20B AH06C AK31C AK70D AK70J AL06D AR00D AT00A BA04 BA07 BA10A BA10D BA13 CA23C EH17D EH66B EJ38A EJ65C GB15 JD02 JK12 A02A02B01A02B02A04B CA07 CA12 DA02 FA03 GA14 HA02 LA01 LA24

Claims (9)

[Claims] Claims: 1. An inorganic oxide vapor-deposited film is provided on one surface of a substrate film, and further, on the inorganic oxide vapor-deposited film,
A barrier film comprising: a primer layer made of a composition containing polyethyleneimine; and a heat-adhesive resin layer further provided on the primer layer. 2. The barrier film according to claim 1, wherein the base film comprises a biaxially stretched resin film or sheet. 3. The barrier property according to claim 1, wherein the inorganic oxide vapor-deposited film comprises a chemical vapor-deposited or physical vapor-deposited inorganic oxide vapor-deposited film. the film. 4. The barrier film according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of silicon oxide formed by a chemical vapor deposition method. 5. The barrier film according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of aluminum oxide formed by physical vapor deposition. 6. The above-mentioned claim, wherein the primer agent layer comprises a coating film of a composition containing polyethyleneimine as a main component of the vehicle and further containing a silane coupling agent and a filler. Item 6. The barrier film according to any one of Items 1 to 5. 7. The barrier film according to claim 1, wherein the heat-adhesive resin layer comprises a resin layer of a copolymer of ethylene-unsaturated carboxylic acid or an ester thereof. . 8. The heat-adhesive resin layer is formed of a copolymer of ethylene-unsaturated carboxylic acid or an esterified product thereof.
The barrier film according to claim 1, comprising a resin layer melt-extruded at 10 ° C. or lower. 9. The heat-adhesive resin layer comprises a copolymer with an ethylene-unsaturated carboxylic acid or an ester thereof, and further comprises an unsaturated carboxylic acid or an ester thereof formed of the copolymer. The barrier film according to any one of claims 1 to 8, comprising a resin layer made of a copolymer containing up to 30 mol%.