JP2001081217A - Barrier film and laminate material using the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film which shows an excellent adhesion between a polyamide resin film and a deposited film of an inorganic oxide, and excellent transparency and an excellent barrier property against oxygen gas, water vapor, or the like, and is useful for packing various articles, e.g. food or beverages, pharmaceuticals, cosmetics, chemicals and a laminate material using the film. SOLUTION: A barrier film A is prepared by forming an anchor coating layer on one side of a polyamide resin film 1 and further forming a deposited film 4 of an inorganic oxide on the surface of the anchor coating layer 3, wherein the polyamide resin film 1 comprises a biaxially oriented nylon film. A laminate material is prepared by dry laminating at least a heat-sealing resin layer via an adhesive layer for dry laminating on the surface of deposited film 4 of an inorganic oxide in the barrier film prepared by forming an anchor coating layer 3 on one side of a polyamide resin film 1 and further forming a deposited film 4 of an inorganic oxide on the surface of the anchor coating 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 a laminated material using the same, and more particularly, to a film having excellent adhesiveness between a polyamide resin film and an inorganic oxide vapor-deposited film, and having high transparency. Excellent in barrier properties against oxygen gas or water vapor, etc., for example, food and drink, pharmaceuticals,
The present invention relates to a barrier film useful for filling and packaging various articles such as cosmetics, chemicals, and others, 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, cosmetics, and others. Among them, in recent years,
As a barrier material against oxygen gas or water vapor, vacuum evaporation is performed using an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc. on the surface of a plastic substrate such as a polyester resin film or a polyamide resin film. Method, sputtering method,
Physical vapor deposition (PVD) such as ion plating
Chemical vapor deposition (CVD), thermal chemical vapor deposition, photochemical vapor deposition, etc.
A barrier film formed by forming a vapor-deposited film of the inorganic oxide by utilizing the above method has attracted attention. Thus, the barrier film is superior to a barrier material composed of a conventional aluminum foil or a polyvinylidene chloride-based resin coat film, etc., in that it is more suitable for incineration and disposal, and is suitable as an environmentally friendly material. In the future, the demand is greatly expected.

[0003]

In the above-mentioned barrier film, a barrier film using a polyamide resin film as a plastic substrate, a barrier film using a polyester resin film or the like as a plastic substrate. Compared with the hydrophilic film, the polyamide resin film has high water absorption,
This causes a phenomenon that water absorbs or adsorbs and swells. Therefore, the vapor deposition film of the inorganic oxide lacks followability to the swelling of the polyamide resin film. There is a problem that microcracks and the like are generated in the deposited film, and the barrier properties and the like are significantly reduced. Further, in some cases, there is a problem that the polyamide resin film as a plastic base material and the vapor-deposited film of the non-periodic oxide lack honey adhesion, and the two peel off and are no longer used. Therefore, in the above barrier film, in order to improve its close adhesion, gas barrier properties, etc., for example, on the surface of a plastic substrate,
In advance, a method of performing a pre-treatment such as a plasma treatment and then forming a vapor-deposited film of an inorganic oxide has been proposed, but the effect thereof can be expected as such.
The reality is that a sufficiently satisfactory barrier film has not yet been produced. Therefore, the present invention
Excellent honey adhesion between the polyamide resin film and the inorganic oxide deposited film, excellent transparency, and excellent barrier properties against oxygen gas or water vapor, for example, food and drink, pharmaceuticals, cosmetics, and chemicals Another object of the present invention is to provide a barrier film useful for filling and packaging various articles such as, and others, and a laminated material using the same.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has found that one side of a polyamide resin film has, for example, an anchor containing a urethane compound as a main component of a vehicle. -Providing an anchor coating agent layer comprising a coating film made of a coating agent, and further providing an inorganic oxide vapor-deposited film on the surface of the anchor coating agent layer to produce a barrier film. Thus, at least a heat-sealing resin layer is provided on the surface of the barrier film on which the inorganic oxide is deposited to produce a laminated material, and then the laminated material is used. Bags are made to produce packaging bags, and then
The contents were packed in the packaging bag, and the opening was heat-sealed to produce a packaged product. The tight adhesion between the polyamide resin film and the inorganic oxide vapor-deposited film was obtained. Excellent, peeling of both, or the occurrence of microcracks and the like is not observed in the deposited film of the inorganic oxide,
It has an extremely high barrier property against oxygen gas or water vapor, etc., and has excellent transparency, and also excellent laminating strength. For example, food and drink, pharmaceuticals, cosmetics, chemicals,
The present invention has been completed by finding that a barrier film useful for filling and packaging various other articles and a laminated material using the same can be produced.

That is, according to the present invention, an anchor coating agent layer is provided on one surface of a polyamide resin film, and an inorganic oxide vapor-deposited film is provided on the surface of the anchor coating agent layer. The present invention relates to a barrier film and a laminate using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of the barrier film according to the present invention and the laminated material using the same will be described with reference to the drawings by exemplifying 12 examples. FIG. 1 shows an example of the barrier film according to the present invention. FIG. 2 is a schematic cross-sectional view showing a layer configuration, and FIG. 2 is a schematic cross-sectional view showing an example of the layer configuration of the laminated material according to the present invention using the barrier film according to the present invention shown in FIG. is there.

First, the barrier film A according to the present invention
As shown in FIG. 1, an anchor coating agent composed of a coating film 2 made of an anchor coating agent containing, for example, a urethane compound as a main component of a vehicle, on one surface of a polyamide resin film 1. Layer 3 is further provided.
The basic structure has a structure in which an inorganic oxide deposited film 4 is provided on the surface of the coating agent layer 3. Thus, in the present invention, as the laminated material B using the barrier film according to the present invention, as shown in FIG. 2, an inorganic oxide vapor-deposited film constituting the barrier film A shown in FIG. 4 is provided with at least a heat-sealing resin layer 5 on its surface. Note that, in FIG.
2, 3 and the like have the same meaning as described above. The above-mentioned illustrations illustrate one or two examples, and the present invention is not limited thereto. For example, although not shown, in the laminated material shown above, the inorganic oxide deposited film 4
For example, a desired printed pattern composed of characters, symbols, figures, patterns, and the like can be provided in advance on the surface.

[0008] Next, in the present invention, the material constituting the barrier film, the laminated material and the like, the production method, and the like according to the present invention will be described. First, in the present invention, as the polyamide resin film, for example, Excellent in strength, heat resistance, especially suitability for retort or boil processing, for example, nylon 46 film, nylon 6 film, nylon 66 film, nylon 610 film, nylon 612 film, nylon 11 film,
Various polyamide resin films or sheets such as a nylon 12 film and the like can be used.
The polyamide-based resin film or sheet may be a single layer, a film formed by a co-extrusion method of two or more layers, or a normal film such as a tenter method or a tuber method. Uniaxial or 2
A film stretched in the axial direction or the like can be used, and the thickness thereof is about 5 to 100 μm, preferably 9 to 50 μm, from the viewpoint of stability during the production of the film.
μm is desirable. Specifically, for example, it is preferable to use a biaxially stretched nylon film or the like.
In the present invention, depending on the application, for example, desired additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, and the like are arbitrarily added within a range not affecting the transparency. A polyamide-based resin film or sheet containing them can also be used.

Next, the anchor coating agent layer in the present invention will be described. The anchor coating agent layer may be, for example, an organic titanium compound, a urethane compound, a polyethyleneimine compound, or a polyethyleneimine compound. A polybutadiene compound as a main component of the vehicle, and further, if necessary, known additives such as a stabilizer, a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber, a filler, and the like are optionally added. Then, a solvent, a diluent and the like are added and mixed well to prepare an anchor coating composition. Thus, in the present invention, the above-mentioned anchor coating composition can be used, for example, in roll coat, gravure roll coat, knife coat, dip coat, spray coat, and others. Coating on the polyamide resin film by the coating method of
After that, the coating film is dried to remove the solvent, diluent and the like.
The agent layer can be formed. In the present invention, the thickness of the coating film constituting the above-mentioned anchor coating agent layer is, for example, about 0.1 to 3.0 g / m ² (in a dry state), preferably 0 to 3.0 g / m ^2. 0.1 to 2.0 g / m ² is desirable.

In the above, examples of the organotitanium compound include tetraisopropyl titanate, tetraisopropyl titanate polymer, and tetrabutyl titanate.
Alkyl titanate such as butyl, tetrabutyl titanate polymer, tetrastearyl titanate, tetrastearyl titanate polymer, and butoxytitanium stearate
Titanium acylate, titanium cetyl acetone, etc.
One or more organic titanium compounds such as titanium chelate such as titanium lactate and the like can be used.

In the above, the urethane compound is, for example, one of a one-pack or two-pack curable urethane compound consisting of a reaction product of a di-polyisocyanate compound and a di-polyoxy compound. Alternatively, two or more kinds can be used. As the di- or polyisocyanate compound, for example, at least an isocyanate compound having two or more isocyanate groups at its terminal or the like or an initial polymer thereof can be used. For example, methylene bis (P
Phenylene diisocyanate), an adduct of hexamethylisocyanate and hexanetriol, hexamethylene diisocyanate, tolylene diisocyanate,
Adduct of tolylene diisocyanate and trimethylolpropane, 1-chlorophenyl-2.4-diisocyanate, 1.5-naphthylene diisocyanate, ethylbenzene-2.4-diisocyanate, 2.4-threlin diisocyanate dimer, 4.4 '. 4 "-triphenylmethane triisocyanate and the like can be used. In the above, the di- or polyoxy compound is an oxy compound having at least two or more hydroxyl groups at its terminal or the like. The prepolymer can be used, and specifically, for example, polyester or its precondensate, polyamide or its precondensate, polyether or its precondensate, poly (meth) acrylic resin, xylene Resins or their initial condensates, epoxy resins or their initial condensates, urethane-modified polyols, etc. Specifically, in the present invention, for example, trimethylolpropane, hexanetriol, Polyoxypropylene polyol, polyether polyol, polyoxy Polyester-based polyols such as tetramethylene glycol, polyadipatepolyol, polycaprolactonediol, polycarbonate-polyol, etc., polybutadienepolyol, polyacrylatepolyol For example, a hydrocarbon-based polyol such as polypropylene, or the like can be used.

In the above, as the polyethyleneimine compound, for example, a polyethyleneimine polymer or the like can be used. Furthermore, the above-mentioned polybutadiene-based compound includes 1.2 bonds or 1.4 bonds.
A polybutadiene polymer or the like comprising a bond or the like can be used.

In the present invention, the anchor coating agent layer is preferably made of, among the above-mentioned compounds, an anchor coating containing a urethane compound as a main component of the vehicle.
When an anchor coating agent layer comprising a coating film is provided by using a coating agent composition, the anchoring agent layer is formed by the extensibility and elasticity of the coating film comprising the urethane-based compound. Through the coating agent layer, the deposited film of the inorganic oxide has a followability to the swelling property of the polyamide-based resin film, and suppresses the occurrence of microcracks and the like in the deposited film of the inorganic oxide. Can also prevent the occurrence of peeling or the like between the polyamide resin film and the deposited film of the inorganic oxide, for example, laminating, or, improve post-processing suitability such as bag making, This is the most desirable anchor coating agent layer because it has the advantage that cracks and the like in the deposited film of the inorganic oxide can be prevented from occurring during post-processing.

Next, in the present invention, a vapor-deposited film of an inorganic oxide will be described. The vapor-deposited film of an inorganic oxide is basically a thin film obtained by making a metal oxide amorphous. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K),
A thin film made of an oxide of a metal such as tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. Can be used. Thus, as a material suitable for a packaging material or the like, a thin film in which an oxide of a metal such as silicon (Si) or aluminum (Al) is made amorphous can be given. Thus,
A thin film obtained by making the above metal oxide amorphous (amorphous) can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide.
Its notation, for example, SiO _X, AlO _X, MO _X (In the formula, M represents a metal element, the value of X, different ranges, respectively, by metal elements.) As such MgO _X in expressed.

The range of the value of X is 0 to 2 for silicon (Si) and 0 to 2 for aluminum (Al).
1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0, potassium (K) is 0-0.5,
Tin (Sn) is 0-2, and sodium (Na) is 0-2.
0.5, boron (B) is 0-1,5, titanium (Ti)
Is 0-2, lead (Pb) is 0-1, zirconium (Z
r) can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 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 the packaging material, generally, except for silicon (Si) and aluminum (Al),
Poorly used examples, silicon (Si) is 1.0 to
As for 2.0 and aluminum (Al), those having a value in the range of 0.5 to 1.5 can be used. In the present invention, as the thickness of the above-described inorganic oxide deposited film,
Depending on the type of metal or metal oxide used, for example, it is, for example, about 50 to 2000 °, preferably 1 to 200 °.
It is desirable to select and form arbitrarily within the range of about 00 to 1000 °. In the present invention, the inorganic oxide vapor deposition film is not limited to one layer of the inorganic oxide vapor deposition film, but may be in the form of a laminate in which two or more layers are laminated. Alternatively, as the metal oxide, one kind or a mixture of two or more kinds can be used to form a deposited film of an inorganic oxide mixed with different materials.

Next, in the present invention, a method for forming an inorganic oxide vapor-deposited film on a polyamide resin film will be described. Examples of the method include a vacuum vapor deposition method, a sputtering method, and an ion plating method. And other physical vapor deposition methods (Physical Vapor D
(e.g., deposition method, PVD method), or a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
Deposition method, CVD method) and the like. In the present invention, the method of forming a vapor-deposited film of an inorganic oxide will be specifically described. The above-described metal oxide is used as a raw material, and a vacuum vapor-deposition method in which this is heated and vapor-deposited on a polyamide-based resin film, Alternatively, an oxidation reaction deposition method in which a metal or metal oxide is used as a raw material, oxygen is introduced and oxidized to deposit on a polyamide-based resin film, and a plasma-assisted oxidation reaction deposition in which the oxidation reaction is further assisted by plasma. The deposited film can be formed by a method or the like. Further, in the present invention, when forming a deposited film of silicon oxide, the deposited film can be formed by a plasma chemical vapor deposition method using organosiloxane as a raw material.

In the present invention, a specific example of a method for forming a vapor-deposited film of an inorganic oxide is shown in FIG. 3. FIG. 3 is a schematic diagram showing an example of a roll-up type vacuum vapor deposition machine. FIG.
As shown in (1), the polyamide resin film 1 is unwound from an unwinding roll 13 in a vacuum chamber 12 constituting a wind-up type vacuum evaporator 11. Next, the polyamide resin film 1 unwound from the unwinding roll 13 passes through the coating drum 14 and is introduced into the vapor deposition chamber 15. Thus, the deposition chamber-1
In 5, the evaporation source (eg, aluminum or aluminum oxide) heated in the crucible 16 is evaporated, and if necessary, oxygen gas or the like is blown out from the oxygen blowing port 17. 15, a mask 18 is provided on one surface of the polyamide-based resin film 1 on the cooled coating drum 14 introduced into
A vapor-deposited film of an inorganic oxide is formed through 18 and then
The polyamide-based resin film 1 on which the inorganic oxide vapor-deposited film is formed is sent out into the vacuum chamber 12 and further wound up on the take-up roll 19 to form the inorganic oxide vapor-deposited film according to the present invention. Can be

Further, in the present invention, a specific example of the above-described plasma chemical vapor deposition method is illustrated. FIG. 4 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus. As shown in FIG. 4, an unloading roll arranged in a vacuum chamber 22 constituting a plasma chemical vapor deposition apparatus 21.
While feeding out the polyamide resin film 1 at a constant speed from the roll 23 through the auxiliary roll 24, the polyamide resin film 1 is cooled and cooled.
It is transported on the peripheral surface of the electrode drum 25. Next, cool down
The polyamide-based resin film 1 is conveyed onto the peripheral surface of the electrode drum 25, and a mixed gas composed of, for example, an organic silicon compound, oxygen gas, an inert gas, or the like, supplied from the raw material volatilizing supply devices 26, 27, and 28 is supplied. It is introduced into the vacuum chamber 22 through the nozzle 29, and the glow discharge plasma 30 is used to deposit a deposited film of an inorganic oxide such as a deposited film of silicon oxide on one surface of the polyamide resin film 1. It is formed and formed into a film. At that time,
A predetermined voltage is applied to the electrode drum 25 from a power supply 31 disposed outside the vacuum chamber 22.
In the vicinity of the cooling / electrode drum 25, a magnet 32 is disposed to promote the generation of plasma, and the deposition of an inorganic oxide deposited film such as a silicon oxide deposited film is prepared. Next, the above-mentioned polyamide resin film 1 on which an inorganic oxide vapor deposition film such as a silicon oxide vapor deposition film is formed can be rolled up on a take-up roll 33 via an auxiliary roll 24 to produce a product. It is. In the figure, reference numeral 33 denotes a vacuum pump.

In the above, the thin film mainly composed of a deposited film of silicon oxide as a deposited film of an inorganic oxide is composed of a silicon compound having at least silicon and oxygen as constituent elements. It contains one or more elements of hydrogen and has a thickness of 100 to 500.
It is preferably within the range of Å. Thus,
In the present invention, as the silicon oxide thin film as described above, an organic silicon compound as a raw material and a deposited film formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like can be used. In the above, as the organic silicon compound, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used . In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its properties and the like. Further, in the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used. In order to obtain the above, it is desirable to use a generator using a high-frequency plasma method.

In the present invention, among the above-mentioned inorganic oxide vapor-deposited films, an aluminum oxide vapor-deposited film formed by a physical vapor deposition method using a roll-up vacuum evaporator or the like is used. The above-mentioned urethane-based compound interacts effectively with an anchor coating agent layer composed of a coating film made of an anchor coating agent containing a vehicle as a main component, and effectively exerts a synergistic effect of both. In particular, it has a favorable effect.

Next, in the present invention, the heat-sealing resin layer will be described. As the heat-sealing resin forming the heat-sealing resin layer, the heat-sealing resin is melted by heat and mutually melted. A resin film or sheet that can be fused can be used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, 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 Polymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as lylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polychlorinated resin A film or sheet of a resin such as a vinyl resin or the like can be used. Thus, in the present invention, a resin film or sheet as described above is used, and this is dry-laminated by a dry laminating method or the like to form a heat-sealing resin layer. Is what you can do. In the present invention, the thickness of the heat-sealing resin layer is preferably about 5 μm to 300 μm, and more preferably about 10 μm to 100 μm.
In the present invention, instead of dry laminating by the above-described dry laminating method or the like, for example, when the above-mentioned polyolefin resin is used and extruded by the extruding laminating method or the like, extrusion is performed. This is undesirable because heat or the like acts during lamination, and cracks and the like are generated in the deposited film of the inorganic oxide.

In the above, when dry laminating, an adhesive for dry laminating can be used, for example, a polyvinyl acetate adhesive, ethyl, butyl, 2-ethylhexyl ester of acrylic acid, etc. Homopolymers, etc., or these and methyl methacrylate,
Acrylonitrile, a polyacrylate adhesive comprising a copolymer of styrene and the like, a cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate,
Ethylene copolymer-based adhesives, cellulose-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, urea resins, or melamine consisting of copolymers with monomers such as acrylic acid and methacrylic acid Amino resin adhesive, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive type (meta) made of resin, etc.
Acrylic adhesive, chloroprene rubber, nitrile rubber,
It is possible to use a rubber-based adhesive made of styrene-butadiene rubber or the like, a silicone-based adhesive, an alkali metal silicate, an inorganic adhesive made of a low-melting glass, or the like, or an adhesive for a dry laminate such as others. Come. The composition of the above-mentioned adhesive for dry laminating may be any composition such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof include a film sheet, a powder, Any form such as a solid form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a hot melt type, and a hot pressure type. The adhesive for dry laminating is applied by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, etc., or a printing method. And the coating amount is 0.1 to 10.0 g / m
² (dry state) is desirable.

In the present invention, among the above-mentioned adhesives for dry laminates, polyurethane-based compounds obtained by reacting the above-mentioned di- or polyisocyanate compounds with di- or polyoxy compounds are the main components. It is desirable to use a one- or two-part curable laminating adhesive. Specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate
Or polyfunctional isocyanates such as aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate.
And polyester ether polyol, polyester polyol
1 to 2 obtained by reaction with a hydroxyl group-containing compound such as phenol, polyacrylate polyol, or the like.
An adhesive composition for a dry laminate containing a liquid-curable polyurethane-based compound as a main component of a vehicle is used. For example, a roll coat, a gravure coat, a knife coat, a dip coat, Coating is performed by spray coating or another coating method, and then a solvent, a diluent or the like is dried to form an adhesive layer for dry laminate. In the above description, the thickness of the adhesive layer for dry laminate is desirably about 0.1 to 6.0 g / m ² (dry state). Thus, in the present invention, by using the polyurethane compound as described above, the core constituting the dry-laminate adhesive layer can be formed in the same manner as described above.
Improves the extensibility, elasticity, etc. of the coating film, for example, improves the post-processing suitability such as lamination processing or bag making processing, and prevents the occurrence of cracks, etc. in the deposited film of inorganic oxide during post-processing. Is what you do.

According to the present invention, the adhesive layer for dry laminating may be formed using a No. 4 dumbbell according to JIS K6301 under an environment of 23 ° C. and 50% RH.
00 mm / min. 300% ~
Preferably, it has a tensile elongation of 550%. In the present invention, the tensile elongation of the above-mentioned adhesive layer is synergistic with the above-mentioned anchor coating agent layer and the like,
It is intended to improve the tight adhesion with the inorganic oxide vapor deposition film, the printed pattern layer, and the like constituting the laminated material, thereby preventing the occurrence of cracks and the like in the inorganic oxide vapor deposition film. In the above, if the tensile elongation is less than 300%, the film lacks flexibility, and cracks or the like are generated in the deposited film of the inorganic oxide in post-processing such as lamination or bag making or box making, which is not preferable. On the other hand, if the tensile elongation exceeds 550%, the flexibility becomes excessive and the tearing property is poor. For example, the openability of the packaging container is poor, which is not preferable. In the present invention, the adhesive composition for a dry laminate containing the polyurethane compound as described above may further include, if necessary, for example, a cellulose derivative such as nitrocellulose, and other binding agents. An agent or the like can be arbitrarily added.

Next, in the present invention, in the laminate according to the present invention, in addition to the above materials,
For example, a resin film or sheet having strength, toughness, and heat resistance can be laminated, and specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, and a polyolefin. Films or sheets of a tough resin such as a base resin, a polycarbonate resin, a polystyrene resin, a polyacetal resin, a fluorine resin, and others can be used. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably 10 μm to 50 μm.
The m-th position is desirable. In the present invention, the base film as described above is subjected to, for example, front printing or back printing by printing a desired printing pattern such as a character, a figure, a symbol, a picture, or a pattern by a normal printing method. It may be.

Next, in the present invention, the laminated material according to the present invention can be laminated, for example, by using various paper base materials constituting a paper layer. As the paper base material, it is provided with shapeability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper base material, pure white roll paper, kraft paper,
Paper substrates such as paperboard and processed paper, and the like can be used. In the above, as the paper base material constituting the paper layer,
Those having a basis weight of about 80~600g / m ² position, preferably, it is desirable to use a basis weight of about 100~450g / m ² position. Of course, in the present invention, the paper substrate constituting the paper layer and the film or sheet of the various resins mentioned above are used.
Can be used in combination.

Further, in the present invention, in the laminated material according to the present invention, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene having a barrier property against water vapor, water, etc. , A film or sheet of a resin such as an ethylene-propylene copolymer, or a resin such as polyvinylidene chloride, polyvinyl alcohol, or a saponified ethylene-vinyl acetate copolymer having a barrier property against oxygen, water vapor, etc. A colorant such as a pigment is added to the film or sheet of the resin, and other desired additives are added and kneaded to form a film. be able to. 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,
About 10 μm to 150 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, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be 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,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film. In the present invention, any one of the layers constituting the laminated material according to the present invention may be formed by, for example, offset printing, gravure printing, silk screen printing, or any other desired method including characters, figures, patterns, symbols, etc. It goes without saying that a print pattern layer can also be formed.

Next, in the present invention, a method of manufacturing a laminated material using the above-described materials will be described.
Examples of such a method include laminating ordinary packaging materials, for example, wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die extrusion molding, and the like. It can be performed by an extrusion lamination method, an inflation method, a co-extrusion inflation method, or the like.
Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film, and for example, an isocyanate-based (urethane) ), Polyethyleneimine-based, polybutadiene-based, organotitanium-based anchor coating agents, or polyurethane-based, polyacryl-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, and other laminating agents. A known pretreatment, such as adhesive for
An anchor coat agent, an adhesive or the like can be used.

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using a laminated material manufactured by such a method, the heat-sealing resin layer of the inner layer is made to face the surface, and it is folded or the two sheets are overlapped, and furthermore, the peripheral edge portion is formed. A bag can be formed by providing a seal portion by heat sealing. Thus, 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,
Further, the peripheral end portion of the outer periphery is formed, for example, by a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket-attached seal type ( According to the present invention, a heat seal is formed according to a heat seal form such as a (pyrro-seale type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. Various forms of packaging containers can be manufactured. Others, for example, self-supporting packaging bags (standing pouches)
And the like can be manufactured, and in the present invention, a tube container and the like can be manufactured using the above-mentioned 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 case of a liquid-filled paper container containing a paper substrate as a packaging container, for example, a laminated material obtained by laminating a paper substrate is produced as a laminated material, and a desired paper container is produced therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head and the like are manufactured using the blank plate to manufacture, for example, a liquid paper container of a brick type, a flat type or a gable-top type. be able to. 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, various types of foods and drinks such as liquid beverages, confectionery, powdery, liquid or solid seasonings, and other adhesives, adhesives and pressure-sensitive adhesives It is used for filling and packaging of various articles such as chemicals, detergents, cosmetics such as others, pharmaceuticals, miscellaneous goods such as chemical warmers, and others. The laminated material according to the present invention can be used as a lid material, for example, by being attached to a flange portion of a plastic molded container.

[0033]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 First, a mixed solvent consisting of toluene, methyl ethyl ketone and isopropyl alcohol in a ratio of 4: 4: 2 was used.
1. urethane compound 8.0% by weight, nitrocellulose
A urethane anchor coating composition containing 0% by weight was prepared. Next, the urethane-based anchor co-
Using a gravure roll coating method on one surface of a biaxially stretched nylon film having a thickness of 15 μm, followed by drying at 120 ° C. for 20 seconds. A coating film (thickness: 0.5 g / m ² , dry state) was formed from the urethane-based anchor coating agent composition to form an anchor coating agent layer. Next, a 200-mm-thick aluminum oxide film is deposited on the above-mentioned anchor coating agent layer by physical vapor deposition (PVD) using a roll-up vacuum vapor deposition machine. Form a film,
A barrier film according to the present invention was produced. Next, on the surface of the aluminum oxide vapor-deposited film of the barrier film produced above, using an ink composition containing a polyurethane resin as a vehicle, a desired print pattern layer consisting of four colors was formed by a gravure printing method. After formation, a dry laminating adhesive composed of a 7% ethyl acetate solution of a two-part curable polyurethane resin composed of polyester polyol and polyisocyanate is used on the entire surface including the printed pattern layer,
This was coated by a gravure roll coating method to form an adhesive layer for dry laminate having a thickness of 1.5 g / m ² (dry state). A low-density polyethylene film having a thickness of 60 μm was used on the surface of the adhesive layer.
Then, a laminated material according to the present invention having the following layer constitution was produced. Biaxially stretched nylon film / anchor coating agent layer / aluminum oxide vapor deposition film / printing pattern layer / dry laminate adhesive layer / low-density polyethylene film The bag was made to produce a three-sided seal-type plastic pouch. Next, the plastic sachet prepared above was filled with the seasoning for powdered ramen, and then the opening was heat-sealed to produce a packaged product. And
Deterioration of the barrier property was not recognized, and an extremely good result was obtained.

Example 2 Using the urethane-based anchor coating composition prepared in Example 1 above, this was used in the same manner as in Example 1 above.
One side of a biaxially stretched nylon film having a thickness of 15 μm is coated by using a gravure roll coating method, and then dried at 120 ° C. for 20 seconds to form the urethane-based anchor coating agent composition. Coating film (0.5g thick)
/ M ² , dry state) to form an anchor coat agent layer. Next, on the anchor coating agent layer provided above, a 200-cm-thick silicon oxide deposited film was formed using a chemical vapor deposition (CVD) method using a plasma chemical vapor deposition apparatus. Was formed to produce a barrier film according to the present invention. Next, on the surface of the vapor-deposited silicon oxide film of the barrier film produced above, an ink composition using a polyurethane-based resin as a vehicle was used in the same manner as in Example 1 above, by a gravure printing method. After a desired printed pattern layer of four colors is formed, dry laminating of a 7% ethyl acetate solution of a two-part curable polyurethane resin composed of polyester polyol and polyisocyanate is applied on the entire surface including the printed pattern layer. Using an adhesive for coating and coating it by a gravure roll coating method to a thickness of 1.5 g
/ M ² (dry state), a low-density polyethylene film having a thickness of 60 μm is used on the surface of the dry-laminate adhesive layer formed above, and the dry-laminate is used. To produce a laminate according to the present invention having the following layer constitution. Biaxially stretched nylon film / anchor coating agent layer / vapor-deposited film of silicon oxide / printed pattern layer / adhesive layer for dry laminating / low density polyethylene film The bag was made to produce a three-sided seal-type plastic pouch. Next, the plastic sachet prepared above is filled with a powdered seasoning for ramen.
When the package was manufactured by heat-sealing the opening, the product had a high level of barrier properties, and no deterioration of the barrier properties was observed.

Comparative Example 1 A biaxially stretched nylon film having a thickness of 15 μm was used, and on the corona-treated surface thereof, a roll-up type vacuum vapor deposition machine was used, and the physical vapor deposition (PVD) method was used. A barrier film was manufactured by forming an aluminum oxide deposited film of 200 °. Next, on the surface of the aluminum oxide vapor-deposited film of the barrier film produced above, using an ink composition containing a polyurethane-based resin as a vehicle in the same manner as in Example 1 above, using a gravure printing method. After a desired printed pattern layer of four colors is formed, dry laminating of a 7% ethyl acetate solution of a two-part curable polyurethane resin composed of polyester polyol and polyisocyanate is applied on the entire surface including the printed pattern layer. -Use adhesive for
This was coated by a gravure roll coating method to form an adhesive layer for dry laminate having a thickness of 1.5 g / m ² (dry state). A low-density polyethylene film having a thickness of 60 μm was used on the surface of the adhesive layer.
Then, a laminated material having the following layer constitution was manufactured. Biaxially stretched nylon film / Aluminum oxide vapor deposited film / Printed pattern layer / Dry laminating adhesive layer / Low density polyethylene film Molded plastic sachets were manufactured. Next, in the plastic pouch produced above,
After filling the powdered seasoning for ramen and then heat-sealing the opening to produce a packaged product, the barrier properties were poor and good results could not be obtained.

Comparative Example 2 A 15-μm-thick biaxially stretched nylon film was used, and its corona-treated surface was first subjected to oxygen plasma treatment in-line using a take-up vacuum vapor deposition machine, followed by oxygen plasma treatment. An aluminum oxide deposited film having a thickness of 200 ° was formed on the surface by physical vapor deposition (PVD) to produce a barrier film. Next, on the surface of the aluminum oxide vapor-deposited film of the barrier film produced above, using an ink composition containing a polyurethane-based resin as a vehicle in the same manner as in Example 1 above, using a gravure printing method. After forming a desired print pattern layer of four colors, a polyester polyol is coated on the entire surface including the print pattern layer.
Using a dry laminating adhesive consisting of a 7% ethyl acetate solution of a two-part curable polyurethane-based resin consisting of toluene and polyisocyanate, and coating it by a gravure roll coating method. A dry-laminate adhesive layer of 1.5 g / m ² (dry state) was formed, and further, on the dry-laminate adhesive layer surface formed above,
Using low-density polyethylene film of thickness 60mμ,
This was dry-laminated to produce a laminated material having the following layer structure. Biaxially stretched nylon film / Plasma treated surface / Evaporated film of aluminum oxide / Printed pattern layer / Adhesive layer for dry laminating / Low density polyethylene film A three-sided sealed plastic pouch was manufactured. next,
The plastic pouches produced above were filled with the powdered seasoning for ramen, and then the opening was heat-sealed to produce a packaged product. Could not be obtained.

Experimental Example 1 The following data were measured for the barrier films produced in Examples 1 and 2 and the barrier films produced in Comparative Examples 1 and 2 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 Permeability This was measured under the conditions of a temperature of 40 ° C. and a humidity of 100% RH with a measuring device (model name, PERMATRAN) manufactured by MOCON, USA. The above measurement results are shown in Table 1 below.

[0038] In Table 1 above, the unit of oxygen permeability is cc / m ^2.
/ Day, and the unit of water vapor permeability is g / m
² / day.

As is evident from the results shown in Table 1 above, the oxygen permeability and the water vapor permeability were measured in Example 1.
-2 were all good, whereas
Each of Comparative Examples 1 and 2 was inferior.

EXPERIMENTAL EXAMPLE 2 The following data were measured for the laminates produced in Examples 1 and 2 and the laminates produced in Comparative Examples 1 and 2 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 the condition under the condition of temperature of 40 ° C. and humidity of 100% RH.
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. (3). Measurement of Laminate Strength Test This was performed using a peel tester (Orientec Co., Ltd., model name, Tensilon universal tester), and a sample of 15 mm
Width, peeling angle 90 degrees, load cell 5 kgf, peeling speed 5
This was performed under the condition of 0 mm / min. The above measurement results are shown in Table 2 below.

[0041] In Table 2 above, the unit of oxygen permeability is cc / m ²
/ Day, and the unit of water vapor permeability is g / m
² / day, and the unit of the laminate intensity is g
f / 15 mm width.

As is evident from the results shown in Table 2 above, the oxygen permeability, the water vapor permeability, and the laminating strength of Examples 1 and 2 were all good. On the other hand, those of Comparative Examples 1 and 2 were all inferior.

[0043]

As is apparent from the above description, the present invention relates to a method of forming a coating film on one side of a polyamide resin film by using, for example, an anchor coating agent containing a urethane compound as a main component of a vehicle. An anchor coating agent layer is provided, and a barrier film is manufactured by further providing an inorganic oxide vapor-deposited film on the surface of the anchor coating agent layer.
At least on the surface of the barrier film on which the inorganic oxide is deposited, a heat-sealing resin layer is provided to produce a laminate,
Next, the laminated material is used, and it is made into a bag to produce a packaging bag. Thereafter, the contents are filled and packaged in the packaging bag, and the opening is heat-sealed. To produce packaging products, excellent adhesion between the polyamide-based resin film and the deposited film of the inorganic oxide, peeling of both, or
No generation of microcracks or the like is observed in the deposited film of the inorganic oxide, and furthermore, it has an extremely high barrier property against oxygen gas or water vapor, and is excellent in transparency, and also excellent in laminating strength and the like. For example, a barrier film useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, and the like, and a laminated material using the same can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a layer configuration of a barrier film according to the present invention.

FIG. 2 is a schematic perspective view showing a layer structure of a laminated material manufactured using the barrier film according to the present invention.

FIG. 3 is a schematic configuration diagram illustrating an example of a take-up type vacuum evaporation machine.

FIG. 4 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polyamide-based resin film 2 Coating film 3 Anchor coating agent layer 4 Deposition film of inorganic oxide 5 Heat-sealing resin layer A Barrier film B Laminate

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) B05D 7/24 302 B05D 7/24 302T 4K029 B32B 7/02 B32B 7/02 7/12 7/12 9/00 9 / 00 A 27/34 27/34 B65D 65/40 B65D 65/40 D C08L 75/04 C08L 75/04 77/00 77/00 C23C 14/08 C23C 14/08 Z F term (reference) 3E086 AD01 BA02 BA04 BA15 BA24 BA33 BA40 BB02 BB05 BB22 CA01 CA28 CA29 CA35 4D075 AE03 BB85Z CA13 CA42 DB53 DC36 EB01 EB38 4F006 AA38 AB03 AB37 BA01 CA07 DA04 4F100 AA17C AA19C AK01D AK06D AK46A AK48ABABACBA BA10BA10 BAK HB31E JD01 JD03 JD04 JL11 JL12D JN01 4J002 AB012 CK021 GH00 HA05 4K029 AA11 AA25 BA44 BB02 BD00 CA01 EA01 FA07 GA03 KA03

Claims (5)

[Claims] An anchor coating agent layer is provided on one surface of a polyamide-based resin film, and a vapor-deposited inorganic oxide film is provided on the surface of the anchor coating agent layer. Barrier film. 2. The barrier film according to claim 1, wherein the polyamide resin film comprises a biaxially stretched nylon film. 3. The coating film according to claim 1, wherein the anchor coating agent layer comprises a coating film made of an anchor coating agent containing a urethane compound as a main component of the vehicle.
3. The barrier film described in any one of items 1 to 2. 4. The barrier film according to claim 1, wherein the deposited film of the inorganic oxide is a deposited film of aluminum oxide formed by physical vapor deposition. 5. A barrier having a structure in which an anchor coating agent layer is provided on one surface of a polyamide resin film, and a vapor-deposited inorganic oxide film is provided on the surface of the anchor coating agent layer. A laminated material characterized in that at least a heat-sealing resin layer is dry-laminated on a surface of a vapor-deposited inorganic oxide film of a conductive film via a dry-laminate adhesive layer.