JP2001315251A - Barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film excellent in transparency and barrier properties for preventing the permeation of oxygen gas, steam or the like, having heat resistance, excellent in printability, laminating processability, bag making processability and other post-treatment processability and useful for packaging food and drink, medicines, cosmetics, chemical products, electronic parts and other various articles, and a laminated material using the same. SOLUTION: The barrier film is obtained by providing a vapor deposition film comprising an inorganic oxide on one surface of a base material film in the vapor deposition chamber of which the vacuum degree is adjusted to 1.0-10-3-1.0×10-2 mbar of a physical vapor phase growing apparatus. The laminated material using the barrier film is disclosed.

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 transparency, barrier properties for preventing permeation of oxygen gas and water vapor and the like, and heat resistance. Printing, laminating
It has excellent suitability for post-processing such as card processing, bag making, etc., and is useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic parts, etc. The present invention relates to a barrier film and a laminated material using the same.

[0002]

2. Description of the Related Art Conventionally, various materials have been developed and proposed as packaging barrier materials for preventing permeation of oxygen gas or water vapor, and one such material is polyethylene terephthalate film. BACKGROUND ART A transparent gas barrier film provided with a deposited film of aluminum oxide on a surface of a plastic substrate by a physical vapor deposition method using a roll-up vacuum deposition apparatus or the like has been developed and proposed.
In this method, the degree of vacuum in the vacuum chamber is usually set at 5.
It is prepared in a range of about 0 × 10 ⁻⁵ mbar to 1.0 × 10 ⁻³ mbar, and metal aluminum or aluminum oxide or the like is used as a deposition material, which is heated by an electron beam heating method or the like. If necessary, a transparent gas barrier film is produced by vapor-depositing aluminum oxide on the surface of a plastic substrate such as a polyethylene terephthalate film while supplying oxygen gas or the like. Thus, the above transparent gas barrier film has one surface,
Alternatively, a laminated material is manufactured by laminating another plastic film, a paper base material, etc. on both sides, and further, using the laminated material, bag-forming or box-forming the packaging material to form various forms of packaging. To manufacture a packaged product, and thereafter, in the packaging container, for example, filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, etc. to produce a packaged product, and supplying it to the market. I have. The above packaged product has a high barrier property of preventing permeation of oxygen gas or water vapor and the like, and is excellent in storage of contents, storage stability, quality assurance, etc., and after use, conventional aluminum foil or Compared to packaging containers and the like using barrier materials such as polyvinylidene chloride-based resin films, it is more suitable for disposal of packaging containers and the like, suitable for environmental protection, and its development and demand are expected in the future. Things.

[0003]

However, in the above-mentioned transparent gas barrier film, the deposited film of aluminum oxide deposited at the above-mentioned degree of vacuum has excellent transparency, and furthermore, oxygen gas, Although it has excellent gas barrier properties to prevent the permeation of water vapor, etc., on the other hand, the film hardness of the deposited aluminum oxide film itself becomes extremely high. As a result, the deposited aluminum oxide film is a vitreous, hard film. In addition, there is a problem that the film becomes inflexible. Thus, the aluminum oxide vapor-deposited film having the above film quality is provided, for example, by providing a primer agent layer on the surface of the aluminum oxide vapor-deposited film, forming a printed pattern or the like thereon, and further, The heat-sealing resin layer and the like are dried through the laminating adhesive layer and the like.
When manufacturing laminated materials as packaging materials,
When forming a primer agent layer, a printed pattern, an adhesive layer for dry lamination, a laminated material, etc., winding, coating, printing, laminating, or the like of the transparent barrier film, or In post-processing such as bag-making, etc., there is a problem that cracks and the like are generated in the deposited film of the inorganic oxide, and accordingly, the barrier property against oxygen gas or water vapor is significantly reduced. Therefore, the present invention is excellent in transparency, barrier properties for preventing permeation of oxygen gas and water vapor, etc., and further has heat resistance, and is subjected to post-processing such as printing, laminating, bag-making, and the like. Has excellent suitability for, for example, food and drink, pharmaceuticals,
An object of the present invention is to provide a barrier film useful for filling and packaging various articles such as cosmetics, chemicals, electronic parts, and the like, and a laminated material using the same.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has used a physical vapor deposition apparatus on one side of a base film, and provided a vapor deposition chamber for the apparatus. -The degree of vacuum inside is 1.0 to 10 ^-3 mbar to 1.0 ×
When a barrier film was manufactured by providing a deposited film of aluminum oxide by adjusting to a range of 10 ⁻² mbar, the deposited film of aluminum oxide formed on one surface of the base film had low crystallinity. A vapor-deposited film that becomes amorphous can be formed, and its film hardness also decreases.For example, when the film is wound on a take-up roll after vapor deposition, contact with a guide roll or the like immediately after vapor deposition, or Winding roll
Prevent the occurrence of microcracks, etc. in contact with the product, etc., and use the manufactured barrier film and apply post-processing such as printing, laminating, bag making, etc. However, generation of cracks or the like is not recognized in the deposited film of aluminum oxide, and a laminated material having an extremely high barrier property against oxygen gas or water vapor can be manufactured.Furthermore, as the deposited film of aluminum oxide, Since it is possible to form a vapor-deposited film with low residual stress, it has heat resistance, and for example, heat-treats a semi-packed body filled with contents using a packaging bag using the above laminated material, such as a retort. However, the resulting change in volume (thermal shrinkage) and the like are small, and the accompanying deterioration of barrier properties can be minimized. For example, food and drink, pharmaceuticals, cosmetics, chemicals , In which an electronic component, and completed the present invention have found that it is possible to produce a laminate using a useful barrier film and it is filling and packaging various articles other like.

That is, in the present invention, a physical vapor deposition apparatus is used on one side of a base film, and the degree of vacuum in a deposition chamber is set to 1.0 to 10 ⁻³ mbar to 1.0 × 10 4
^The present invention relates to a barrier film having an inorganic oxide vapor-deposited film adjusted to a range of ^-2 mbar, and a laminated material using the same.

[0006]

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

As shown in FIG. 1, a barrier film A according to the present invention uses a physical vapor deposition apparatus on one surface of a base film 1 and sets the degree of vacuum in a deposition chamber to 1.degree. in that it consists of 0-10 adjusted to a range of ^{-3 mbar~1.0} × 10 ^-2 mbar providing a deposition film 2 of an inorganic oxide structure are those having a basic structure. Thus, in the present invention, as the laminate B using the barrier film A according to the present invention, as shown in FIG. 2, an inorganic oxide constituting the barrier film A shown in FIG. Has a basic structure in which at least a heat-sealing resin layer is laminated on the surface of the deposited film 2.
In FIG. 2, reference numeral 1 has the same meaning as in FIG. The above examples are barrier films according to the present invention,
This is merely an example of a laminated material and the like, and it goes without saying that the present invention is not limited thereto.

Next, in the present invention, the materials constituting the barrier film, the laminated material, etc. according to the present invention and the manufacturing method thereof will be described. First, the barrier film, the laminated material, etc. according to the present invention will be described. As a constituent base film, it has excellent chemical or physical strength, withstands the conditions for forming a vapor-deposited film of an inorganic oxide described below, and keeps it well without impairing the properties of the vapor-deposited film of the inorganic oxide. Substrates can be used. In the present invention, specifically, as the base film,
For example, polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (Meta)
Acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polyamide resin such as various nylons, polyurethane resin, fluorine resin, acetal resin Films or sheets of various resins such as resin, cellulose resin and others can be used. In the present invention, among the resin films or sheets described above,
In particular, it is preferable to use a film or sheet of a polyester resin, a polyolefin 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 200 μm.
And more preferably about 9 to 100 μm.

[0010] One or more of the above various resins are used, and when forming the film, 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,
An antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

Next, in the present invention, the vapor-deposited inorganic oxide film constituting the barrier film, the laminated material and the like according to the present invention will be described. Any thin film can be used as long as it is an amorphous (amorphous) thin film of an oxide of, for example, silicon (Si), aluminum (Al), magnesium (M
g), calcium (Ca), potassium (K), tin (S
n), sodium (Na), boron (B), titanium (T
A thin film in which a metal such as i), lead (Pb), zirconium (Zr), or yttrium (Y) or an oxide of the metal is made amorphous (amorphous) can be used. Thus, as a material suitable for a packaging material or the like, a thin film obtained by converting a metal such as aluminum (Al) or an oxide of a metal such as silicon (Si) or aluminum (Al) into an amorphous material is used. Can be mentioned. Thus, a thin film obtained by converting the above metal oxide into an amorphous (amorphous)
It can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and the notation is, for example, MO _x (wherein, in the formula, SiO _x , AlO _x , MgO _x, etc.) M represents a metal element, and the value of X varies depending on the metal element.)

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, not transparent, and the upper limit of the range of X is a completely oxidized value. In the present invention,
As a packaging material, generally, there are few examples of use except for silicon (Si) and aluminum (Al). Silicon (Si) is 1.0 to 2.0, aluminum (Al)
Can be used in the range of 0.5 to 1.5.

In the present invention, the thickness of the above-mentioned inorganic oxide vapor-deposited film varies depending on the type of the metal or the metal oxide used, and is, for example, 50 to 200.
It is desirable to arbitrarily select and form it within the range of 0 °, preferably 100 to 1000 °. More specifically, in the case of a deposited film of aluminum oxide or silicon oxide, the thickness is preferably about 50 to 500 °, more preferably about 100 to 300 °. In the above film thickness, when the film thickness is smaller than the above film thickness, it is not preferable because the barrier property against oxygen gas, water vapor and the like is reduced, and when the film thickness is larger than the above film thickness, During the post-processing step, cracks and the like are generated in the deposited film of the metal or metal oxide, the barrier property against oxygen gas, water vapor and the like is remarkably reduced, and the close adhesion to the base film is further reduced. Not something.

Next, in the present invention, a method for forming a vapor-deposited film of an inorganic oxide on one surface of a substrate film will be described. Examples of the method include a vacuum vapor deposition method, a sputtering method, and an ion pre-deposition method. -Physical vapor deposition method such as a plating method
position method, PVD method) and the like. In the present invention, the method for forming the inorganic oxide vapor-deposited film will be specifically described. The above-described metal or metal oxide is used as a raw material, and is heated and vapor-deposited on one surface of the base film. Vacuum evaporation method, or oxidation reaction deposition method of using a metal or metal oxide as a raw material, introducing oxygen gas or the like, oxidizing and depositing on one surface of the base film, and further oxidizing reaction The deposited film can be formed using a plasma-assisted oxidation reaction evaporation method assisted by plasma or the like.

In the present invention, the method of forming the above-mentioned vapor-deposited film of inorganic oxide will be described with reference to specific examples.
FIG. 3 is a schematic configuration diagram illustrating an example of a take-up type vacuum evaporation apparatus. As shown in FIG. 3, first, the substrate film 1 is unwound from an unwinding roll 13 in a vacuum chamber 12 constituting a winding type vacuum evaporation apparatus 11. Next, the base film 1 unwound from the unwinding roll 13 passes through the coating drum 14 and is guided into the deposition chamber 15. On the other hand, evaporation 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 vapor-deposited film of an inorganic oxide is formed on one surface of the base film 1 on the cooled coating drum 14 through the masks 18, 18. The substrate film 1 on which the oxide film was formed was placed in a vacuum chamber-1.
2 and then wound up on a take-up roll 19, the inorganic oxide deposited film according to the present invention can be formed. In the present invention, immediately before the base film 1 is guided into the vapor deposition chamber 15, a plasma processing apparatus 20 is provided as a pre-processing unit. On one surface of the substrate film 1, a plasma-treated surface is formed by performing sufficient plasma processing in advance, and then the base film 1 is guided into the deposition chamber 15, and one of the base films is formed in the same manner as described above. A vapor-deposited film of an inorganic oxide may be formed on the surface.

In the present invention, when the inorganic oxide vapor deposition film is formed using the above-mentioned roll-up type vacuum vapor deposition apparatus or the like, the degree of vacuum in the vapor deposition chamber is set to 1.0 to 1.0. The method is characterized in that the inorganic oxide vapor-deposited film is provided so as to be adjusted to a range of 10 ⁻³ mbar to 1.0 × 10 ⁻² mbar. Thus, in the present invention, as described above, the degree of vacuum in the deposition chamber is set to 1.0 to 10 ⁻³ mbar to 1.0 × 10 ⁻² mbar on one surface of the base film.
By providing a deposited film of aluminum oxide by adjusting the range of the above, the deposited film of aluminum oxide formed on one surface of the base film can form a more amorphous deposited film having low crystallinity. The film hardness is also reduced. For example, when the film is wound on a take-up roll after vapor deposition, the film comes into contact with a guide roll or the like immediately after vapor deposition or with a take-up roll. Can prevent the occurrence of microcracks and the like. Further, using the barrier film produced above, on the surface of the inorganic oxide deposited film, for example, printing, laminating
No cracks are observed in the deposited aluminum oxide film even after post-processing such as bag processing, bag making, etc., and a laminated material having an extremely high barrier property against oxygen gas or water vapor is produced. Is what you can do. In addition, as a deposited film of aluminum oxide provided on one surface of the base film, since a deposited film having a small residual stress can be formed, it has heat resistance and, for example, the above-described laminated material was used. Even if a semi-packed body filled with contents using a packaging bag is subjected to high-temperature treatment such as retort,
The change in volume (thermal shrinkage) and the like caused thereby are small, and the deterioration of the barrier property and the like accompanying the change can be minimized. Further, in the present invention, when forming a deposited film of an inorganic oxide, the degree of vacuum in the deposition chamber is adjusted to a range of 1.0 to 10 ⁻³ mbar to 1.0 × 10 ⁻² mbar. Thus, the evacuation time before vapor deposition can be shortened, so that the productivity and the like of the barrier film can be significantly improved.

In the present invention, the base film is
Immediately before being guided into the deposition chamber, a plasma processing apparatus is provided as a pre-processing unit, and the plasma processing apparatus performs sufficient plasma processing on one surface of the base film in advance to perform plasma processing. The method for forming a surface will be described. First, as the above-mentioned plasma-treated surface, a plasma surface treatment method or the like for performing surface modification using a plasma gas generated by ionizing a gas by glow discharge is used. Thus, a plasma processing surface can be formed. That is, in the present invention, the plasma treatment is performed by a method using one or more kinds of inorganic gases such as oxygen gas, nitrogen gas, argon gas, and helium gas as the plasma gas to form the plasma treatment surface. Can be. Thus, in the present invention, as the plasma treatment performed on the surface of the base film, the plasma treatment is performed using an oxygen gas or a mixed gas of an oxygen gas and an argon gas during the plasma discharge treatment. It is preferable that the plasma treatment can be performed at a lower voltage by such a plasma treatment, thereby preventing discoloration or the like of the surface of the base film, and forming a good plasma treatment surface on the surface. It can be provided.

In the present invention, oxygen plasma or a mixed gas of oxygen gas and argon gas is used as the plasma treatment, and the surface of the base film is made of metal or metal oxide. It is desirable to carry out the process in-line immediately before forming the deposited film. That is, in the present invention, the base film is mounted on, for example, a supply roll or the like in a roll-up type vacuum deposition apparatus, and an inorganic oxide deposited film is formed on one surface of the base film. Immediately before, by performing in-line plasma treatment, moisture and dust attached to one surface of the base film are removed, and furthermore, oxygen molecules and the like activated in the plasma are removed from the base film. By causing a chemical reaction with the surface, a plasma-treated surface having a thin, highly smooth oxide film or the like formed on the treated surface can be provided. Further, in the present invention, by performing in-line plasma treatment immediately before forming the inorganic oxide vapor-deposited film on the surface of the substrate film, for example, a hydroxyl group (-OH group) It is also possible to provide a plasma processing surface on which a surface or the like is formed.

In the present invention, an oxide film is formed on the surface of the base film by the plasma treatment as described above.
Alternatively, when a vapor-deposited film of an inorganic oxide is formed by vapor deposition on the plasma-treated surface on which a hydroxyl group (-OH group) or the like is formed as described above, impurities such as impurities may be interposed between the layers. And a very dense metal or inorganic oxide deposited film can be formed, and both have excellent close-adhesion properties, and as a result, have a thin film thickness and are sufficiently resistant to oxygen gas or water vapor. It can form a high barrier thin film. Moreover, in the present invention, as described above, the inorganic oxide vapor-deposited film can be formed with a smaller thickness to sufficiently form a high-barrier thin film against oxygen gas or water vapor.
For example, in the post-processing such as film winding, printing, laminating, or bag-making, it is possible to prevent the occurrence of cracks and the like in the above-described inorganic oxide vapor-deposited film. It also has the advantage that the suitability for post-processing can be improved. Further, in the present invention, as described above, since the close adhesion between the base film and the inorganic oxide vapor-deposited film is excellent, the laminating suitability of a film or sheet of another resin is also improved. It will improve. Further, in the present invention, since the plasma treatment is performed in-line immediately before the formation of the vapor-deposited film of the inorganic oxide on the surface of the base film, the production cost of the barrier film is also lower than other methods. It is very good.

In the present invention, in the above-described plasma processing, the plasma processing conditions are extremely important, and the effects obtained by the conditions are completely different. Thus, in the present invention, the plasma processing conditions include plasma discharge power, glow discharge pressure, and the like. In the present invention, the plasma processing includes:
For example, the stronger the plasma treatment, the better the tight adhesion is, but if it is too strong, the base film is not preferable because it loses heat. Thus, in the present invention, as the plasma discharge power, Is about 40 W · min / m ²
The order of １００100 W · min / m ² is most preferable. In the present invention, the plasma power source may be AC or DC, and the glow discharge pressure may be set to 0.1 or less.
It is preferably about 5 to 5.0 × 10 ⁻² mbar. In a very high vacuum, the stability of the plasma is lacking.
This is not preferable because the effect of the plasma on the base film is weakened.

In the present invention, as a method of generating plasma in the plasma processing, for example, DC glow discharge, high frequency (Audio Frequ
ency: AF, Radio Frequency: R
F) It can be performed using three types of devices such as discharge and microwave discharge. In the present invention, a plasma-treated surface formed by the above-described plasma treatment on the surface of the base film immediately before the formation of the inorganic oxide vapor-deposited film was subjected to X-ray photoelectron spectroscopy manufactured by VG Scientific, UK. By performing elemental analysis on the treated surface using an analytical measuring device (model name, XPS), as described above, moisture and dust attached to the surface of the base film can be removed,
Further, the oxygen-activated molecules activated in the plasma cause a chemical reaction with the surface of the base film, thereby forming a thin and highly smooth oxide film on the treated surface. On the surface of the material film, for example,
It can be confirmed that the surface is a plasma-treated surface on which a functional group such as a hydroxyl group (-OH group) is formed. Specifically, the X-ray source is MgKα1.2, the X-ray output is 15 Kv, and the surface is 10 to 20 mA under the measurement conditions of 20 mA.
XPS analysis at 0 ° is performed, and the formation state of the oxide film can be confirmed by measuring the composition ratio of O / C (oxygen and carbon) on the surface. state of formation, peak obtained 532eV position of O1 _S - in which can be confirmed by measuring the click.

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 the above-mentioned roll-up type vacuum vapor deposition apparatus is used. Interacts effectively with the above-mentioned plasma-treated surface, exhibits a synergistic effect by both of them, and can produce a barrier film in which a base film and an aluminum oxide vapor-deposited film are firmly and closely adhered. It is. In particular, in the present invention, as described above, immediately before the deposition of the aluminum oxide deposition film in-line, a plasma treatment is performed to form a plasma-treated surface, and the tight adhesion between the base film and the aluminum oxide deposition film is obtained. It is something that has been improved.

Next, in the present invention, the heat-sealing resin layer constituting the laminated material manufactured using the barrier film according to the present invention will be described. Can be used as a heat-sealing resin film or sheet. In the present invention, as the heat-sealing resin film or sheet, specifically, a resin film or sheet which can be melted and fused to each other by heat can be used. For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-α-olefin copolymer polymerized using a single-site catalyst (metallocene catalyst),
Polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer,
Polyolefin resins such as ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene are converted to unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid. A resin film or sheet of an acid-modified acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride 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. Alternatively, in the present invention, a heat-sealing resin layer is formed by extruding the heat-sealing resin or the like using the above-mentioned heat-sealing resin or the like by an extrusion laminating method or the like. You can also. In the present invention, the thickness of the heat-sealing resin layer is preferably about 5 μm to 300 μm,
Further, the thickness is preferably about 10 μm to 100 μm.

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, one-pack containing, as a main component, a polyurethane compound obtained by reacting a di- or polyisocyanate compound with a di- or polyoxy compound. It is desirable to use a two-part curing type adhesive for laminating. Specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate
Aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate, or polyfunctional isocyanates such as aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate; Polyether 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 above-mentioned polyurethane compound, the extensibility, elasticity, etc. of the coating film constituting the adhesive layer for dry laminating are improved, and for example, the laminating compound is used. The purpose of the present invention is to improve the suitability for post-processing such as processing or bag making, and to prevent the occurrence of cracks and the like in the deposited film of inorganic oxide during the post-processing.

In the present invention, the adhesive layer for dry laminating may be formed with a No. 4 dumbbell according to JIS K6301 at 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 adhesive layer is a vapor-deposited film of an inorganic oxide constituting a laminate,
It is intended to improve the tight adhesion with the printed pattern layer and the like, thereby preventing the occurrence of cracks and the like in the deposited film of the inorganic oxide. 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. , And the tensile elongation,
If it exceeds 550%, the flexibility is 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.

In the present invention, when the above-described extrusion lamination is performed, if necessary, for example, isocyanate-based (urethane-based), polyethyleneimine-based,
An anchor coating agent of polybutadiene type, organic titanium type or the like can be used. In the present invention,
The above-mentioned anchor coating agent is, for example, roll-coated
Coating, gravure coating, knife coating, dip coating, spray coating and other coating methods, and then drying the solvent, diluent, etc.
A coating agent layer can be formed. In the above, the thickness of the anchor coating agent layer is 0.1 to 6.0 g /
m ² (dry state) is desirable.

Next, in the laminate according to the present invention, for example, a resin film or sheet having strength and toughness and heat resistance can be laminated. For example, polyester resins, polyamide resins, polyaramid resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyacetal resins, fluorine resins, and other tough resins Films, sheets, etc. 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
About 50 μm 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.

In the laminated material according to the present invention,
For example, it can be laminated using various paper base materials constituting a paper layer. Specifically, in the present invention, the paper base material has moldability, bending resistance, rigidity, and the like. For example, a strong size bleached or unbleached paper substrate, a paper substrate such as pure white roll paper, kraft paper, paperboard, processed paper, and the like can be used. In the above,
As the paper base material constituting the paper layer, the basis weight is about 80 to 600 g.
/ M ² , preferably about 100-450 g of grammage
/ M ² . Of course, in the present invention, a paper base constituting the paper layer and a film or sheet of the above-mentioned various resins 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 for producing a laminated material using the above-mentioned 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
Known pre-treatments such as adhesives for laminates such as lacquer-based and others, anchor coat agents, adhesives and the like can be used. Furthermore, in the present invention, when the above-mentioned lamination is performed, for example, a primer containing a polyurethane-based, polyacryl-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, or the like as a main component of the vehicle is used. -Agents and the like can also 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 in which a paper substrate is laminated 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, in particular, when manufacturing the above-mentioned paper container or the like, the foldability and engraving ability for engraving the crease lines and the like can be remarkably improved, thereby improving the sealing failure and the like. It is possible to improve the stability of the seal in the seal portion.

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.

[0036]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 (1). A take-up type vacuum evaporation apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. First, 2
Using aluminum as a vapor deposition source, an electron beam is applied to the roll of the axially stretched polyethylene terephthalate film on the delivery roll of a take-up type vacuum evaporation apparatus, and then to the corona treated surface of the biaxially stretched polyethylene terephthalate film.
(EB) While supplying oxygen gas by a reactive vacuum deposition method using a heating method, a film thickness of 20
A barrier film according to the present invention was manufactured by forming a 0 ° aluminum oxide deposited film. (Deposition conditions) Degree of vacuum in deposition chamber: 3.5 × 10 ⁻³ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 35 kW Film transport speed: 600 m / min Deposition surface: Corona treated surface (2). Next, a primer composition (trade name: PD-4, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used on the aluminum oxide vapor-deposited film surface of the barrier film produced above by a gravure roll coating method. To a thickness of 0.
A primer layer of 02 g / m ² (dry state) was formed, and a two-component curing type polyurethane-based dry laminate adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, Takerack A-515 / Takenate A
-50) by gravure roll coating.
To form a dry-laminate adhesive layer having a thickness of 4.0 g / m ² (dry state), and then apply a 50 μm-thick low-density polyethylene film to the dry-laminate adhesive layer surface. To produce a laminate according to the present invention. In addition, using the above laminated material, a three-sided seal type flexible packaging bag was manufactured, and sprinkled with the sprinkle and the like to manufacture a packaged product. As a result, the product was sufficiently distributed, stored, and sold in the market. It was tolerable.

Embodiment 2 (1). A take-up type vacuum evaporation apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. One surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as the base film was previously subjected to a corona discharge treatment, and had a static and dynamic friction coefficient of 0.60 μm, respectively. , 0.56μ. First,
The above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a delivery roll of a take-up type vacuum evaporation apparatus so that the non-corona treated surface is vapor-deposited. On the non-corona treated surface, that is, the other surface, a plasma treatment was performed in-line using a discharge plasma generator under the following conditions to form a plasma treated surface. (Plasma treatment conditions) Glow-discharge gas: oxygen gas Power supply: DC Discharge power: 60 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma treatment surface: non-corona treatment surface Then, in-line plasma After forming the treated surface, the plasma treated surface is supplied with oxygen gas using aluminum as a deposition source, and is subjected to a reactive vacuum deposition method using an electron beam (EB) heating method under the following deposition conditions.
Forming a deposited film of aluminum oxide with a thickness of 200 °,
A barrier film according to the present invention was produced. (Evaporation conditions) Degree of vacuum in evaporation chamber: 4.5 × 10 ⁻³ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 30 kW Film transport speed: 480 m / min Deposition surface: Plasma treated surface (2). Next, a primer composition (trade name: PD-4, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used on the aluminum oxide vapor-deposited film surface of the barrier film produced above by a gravure roll coating method. To a thickness of 0.
A primer layer of 02 g / m ² (dry state) was formed, and a two-component curing type polyurethane-based dry laminate adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, Takerack A-515 / Takenate A
-50) by gravure roll coating.
To form a dry-laminate adhesive layer having a thickness of 4.0 g / m ² (dry state), and then apply a 50 μm-thick low-density polyethylene film to the dry-laminate adhesive layer surface. -I did it. On the other hand, on the corona-treated surface of the biaxially stretched polyethylene terephthalate film of the barrier film produced above, a two-component curable polyurethane-based dry laminating adhesive (Takelac A manufactured by Takeda Pharmaceutical Co., Ltd.) -515 / Takenate A-50) to form an adhesive layer for dry laminate having a thickness of 4.0 g / m ² (dry state) by coating by a gravure roll coating method. And then
On the surface of the adhesive layer for dry laminating, a 25 μm thick 2
The laminated material according to the present invention was manufactured by dry laminating the axially stretched polypropylene film. In addition, a three-sided seal type flexible packaging bag was manufactured using the above-described laminated material, and then packed with soy sauce, source, and the like to manufacture a packaged product. As a result, distribution, storage, and sale in the market were performed. And so on.

Embodiment 3 (1). A take-up type vacuum evaporation apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. First, 2
Using aluminum as a vapor deposition source, an electron beam is applied to the roll of the axially stretched polyethylene terephthalate film on the delivery roll of a take-up type vacuum evaporation apparatus, and then to the corona treated surface of the biaxially stretched polyethylene terephthalate film.
(EB) While supplying oxygen gas by a reactive vacuum deposition method using a heating method, a film thickness of 20
A barrier film according to the present invention was manufactured by forming a 0 ° aluminum oxide deposited film. (Deposition conditions) Degree of vacuum in deposition chamber: 3.5 × 10 ⁻³ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 35 kW Film transport speed: 600 m / min Deposition surface: Corona treated surface In order to stabilize the oxygen plasma gas state during the above-mentioned deposition, 1000 sccm at a pressure of 3 kgf / cm ^2.
Ar gas was inserted. (2). Next, a low-density polyethylene was used on the aluminum oxide-deposited film surface of the barrier film manufactured above using a T-die and as an extruding resin, and the above low-density polyethylene was extruded at an extrusion temperature of 295 ° C. While melt-extruding to a thickness of 15 μm, an unstretched polypropylene film having a thickness of 20 μm is extruded and laminated,
A laminate according to the present invention was manufactured. Using the laminated material, a three-sided seal type soft packaging bag is manufactured, and a hamburger is filled and packaged to manufacture a semi-finished packaging product. The packaged product was manufactured by performing a retort treatment at 30 ° C. for 30 minutes. The packaged product manufactured as described above was sufficiently resistant to distribution, storage, sale, and the like in the market.

Embodiment 4 (1). Using a roll-up type vacuum evaporation apparatus, and using a biaxially stretched nylon 6 having a thickness of 15 μm as a base film.
Film was used. First, the above biaxially stretched nylon 6
The film was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then a reaction was performed on the corona-treated surface of the biaxially stretched nylon 6 film by an electron beam (EB) heating method using aluminum as an evaporation source. An aluminum oxide deposited film having a thickness of 200 ° was formed by a vacuum deposition method under the following deposition conditions to produce a barrier film according to the present invention. (Evaporation conditions) Degree of vacuum in evaporation chamber: 3.5 × 10 ⁻³ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 30 kW Film transport speed: 480 m / min Deposition surface: Corona treated surface (2). Next, a primer composition (trade name: PD-4, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used on the aluminum oxide vapor-deposited film surface of the barrier film produced above by a gravure roll coating method. To a thickness of 0.
A primer layer of 02 g / m ² (dry state) was formed, and a two-component curing type polyurethane-based dry laminate adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, Takerack A-515 / Takenate A
-50) by gravure roll coating.
To form a dry-laminate adhesive layer having a thickness of 4.0 g / m ² (dry state), and then apply a 50 μm-thick low-density polyethylene film to the dry-laminate adhesive layer surface. -I did it. On the other hand, on the surface of the biaxially stretched nylon 6 film of the barrier film produced above, a two-component curable polyurethane dry laminator
Adhesive (product name, Takerac A-515 / Takenet A-50, manufactured by Takeda Pharmaceutical Co., Ltd.)
By coating by a gravure roll coating method, an adhesive layer for dry laminate having a film thickness of 4.0 g / m ² (dry state) was formed. A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was dry-laminated to produce a laminate according to the present invention. In addition, a three-sided seal type flexible packaging bag was manufactured using the above laminated material, and ham and sausage etc. were filled and packaged to manufacture a packaged product. , And could withstand sales and the like.

Comparative Example 1 (1). A take-up type vacuum evaporation apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. First, a biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a take-up type vacuum evaporation apparatus.
On the corona-treated surface of the axially stretched polyethylene terephthalate film, a reaction vacuum deposition method using an electron beam (EB) heating method using aluminum as an evaporation source was performed while supplying oxygen gas under the following evaporation conditions. ,
A barrier film was manufactured by forming a 200 ° -thick aluminum vapor-deposited film. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2.5 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 35 kW Film transport speed: 600 m / min Deposition surface: Corona treated surface (2). Next, using the barrier film produced above, the same procedure as in Example 1 above was used. First, the primer composition (Dainichi Seimitsu) was applied to the aluminum film of the barrier film produced above. A primer layer having a film thickness of 0.02 g / m ² (dry state) was formed by coating using a gravure roll coating method using a trade name PD-4) manufactured by Kako Kogyo Co., Ltd. The surface of the primer layer is coated with a gravure adhesive using a two-component curable polyurethane-based dry laminating adhesive (product name, Takelac A-515 / Takenate A-50, manufactured by Takeda Pharmaceutical Co., Ltd.). Coating by a coating method to form a film thickness of 4.
An adhesive layer for dry lamination of 0 g / m ² (dry state) was formed, and then a low-density polyethylene film having a thickness of 50 μm was dry-laminated on the surface of the adhesive layer for dry lamination to form a laminate. Manufactured. In addition, a three-sided seal type soft packaging bag was manufactured by using the above-mentioned laminated material, and a sprinkle or the like was filled and packaged to manufacture a packaged product.

Comparative Example 2 (1). Use a rewind-type vacuum evaporation system and
12μm thick biaxially stretched polyethylene
A terephthalate film was used. The above group
12μm-thick biaxially stretched polyethylene as material film
On one side of the terephthalate film,
With static discharge and dynamic friction coefficient
Were 0.60 μ and 0.56 μ. First,
The above biaxially stretched polyethylene terephthalate film
The delivery roll of the take-up type vacuum evaporation system
Mount so that the corona treated surface is deposited, then
Non-corona treatment of stretched polyethylene terephthalate film
Surface, i.e., in-line discharge plasma
Plasma processing was performed using the laser generator under the following conditions.
A plasma-treated surface was formed. (Plasma processing conditions) Glow discharge gas: oxygen gas Power supply: DC Discharge power: 60 W · min / m^Two Glow discharge pressure: 2.0 × 10^-2mbar plasma treated surface: non-corona treated surface Then, after forming the plasma treated surface in-line,
Aluminum is used as the evaporation source on the plasma treated surface, and oxygen
Supplying gas and using electron beam (EB) heating
By the reaction vacuum deposition method, according to the following deposition conditions,
Forming a deposited film of aluminum oxide with a thickness of 200 °,
A barrier film was manufactured. (Evaporation conditions) Degree of vacuum in evaporation chamber: 5.0 × 10^-Fourmbar The degree of vacuum in the take-up chamber: 2 × 10^-2mbar Electron beam power: 35 kW Film transport speed: 480 m / min Evaporation surface: Corona treated surface (2). Next, use the barrier film produced above
Thereafter, in the same manner as in Example 2 described above,
Aluminum oxide deposited film surface of barrier film produced
, A primer composition (manufactured by Dainichi Seika Kogyo Co., Ltd.
Using the name PD-4) and the gravure roll coating method.
After coating, a film thickness of 0.02 g / m^Two(Dry
Forming a primer layer, and further comprising
For two-component curing type polyurethane dry laminate on the surface
Adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, bamboo rack
 A-515 / Takenate A-50)
3. Coated by a via roll coating method to obtain a film thickness of 4.
0 g / m^Two(Dry state) adhesive layer for dry laminate
And then the surface of the adhesive layer for dry laminating
A 50 μm-thick low-density polyethylene film
I was illuminated. On the other hand, the barrier
Film biaxially stretched polyethylene terephthalate film
Surface, two-component curing type polyurethane dry laminate
Adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, Takera
A-515 / Takenate A-50)
Coating by the lab roll coating method, the film thickness
4.0 g / m ^TwoAdhesion for dry laminate (dry state)
Forming an adhesive layer, and then the adhesive layer for dry laminating.
25μm thick biaxially oriented polypropylene film on the surface
Was subjected to dry lamination to produce a laminated material. In addition, above
Manufactures three-sided seal type flexible packaging bags using the above laminated materials
Then, the product is packed with soy sauce, sauce, etc. to produce a packaged product.
Built.

Comparative Example 3 A roll-up type vacuum evaporation apparatus was used, and
And a 12 μm thick biaxially stretched polyethylene terephthalate
2 using the same film as in Comparative Example 1 above.
On one side of the axially stretched polyethylene terephthalate film,
An aluminum oxide deposited film having a thickness of 200 ° was formed.
Next, on the aluminum oxide deposited film surface formed above,
Two-component curable polyurethane dry glue adhesive
(Takeda Pharmaceutical Co., Ltd., product name, Takerack A-
515 / Takenate A-50)
Coating by a coating method to obtain a film thickness of 4.0 g /
m^Two(Dry) adhesive layer for dry lamination
Then, on the surface of the adhesive layer for dry laminating,
Dry laminating a 15 μm biaxially stretched nylon 6 film
-I did it. Further, the above-described dry-laminated biaxial stretching
On the surface of the nylon 6 film, apply a two-component hard
Adhesive for polyurethane dry laminate (Takeda
Product name, bamboo rack A-515 manufactured by Yakuhin Kogyo Co., Ltd.
/ Takenate A-50) to prepare gravure rolls
Coating by the coating method to a film thickness of 4.0 g / m
^Two(Dry) adhesive layer for dry lamination
Then, on the surface of the adhesive layer for dry laminating,
Dry stretched 60μm unstretched polypropylene film
The laminate was manufactured by mining. The above laminated material
To produce a three-sided seal-type flexible packaging bag,
To produce semi-finished products by filling and packaging
Then, the packaged semi-finished product is retorted at 120 ° C. for 30 minutes.
To produce a packaged product.

EXPERIMENTAL EXAMPLES Using the barrier films and the laminates produced in Examples 1 to 4 and Comparative Examples 1 to 3, tests were performed on the following evaluation items, and the data were obtained. Was measured. (1). Measurement of Oxygen Permeability Using a barrier film and a laminated material manufactured as described above, at a temperature of 23 ° C. and a humidity of 90% RH, a measuring device [model name, Oxtran (Mocon) manufactured by MOCON, USA) OXTRAN 2/20)]. (2). Measurement of Water Vapor Permeability Using a barrier film and a laminated material manufactured as described above, at a temperature of 37.8 ° C. and a humidity of 100% RH, a measuring machine manufactured by MOCON, USA [model name, Par
Matran (PERMTRAN 2/20)]. (3). Measurement of Laminate Strength Laminate strength was measured at a T-peel strength at a tensile speed of 50 mm / min with a tensile tester using a sample obtained by cutting each of the laminated materials produced as described above into strips having a width of 15 mm. Was done. The above measurement results are shown in Table 1 below.

[0044] In Table 1 above, the unit of oxygen permeability is (cc / m
² day 23 ° C. 90% RH), and the unit of water vapor permeability is (g / m ² day 40 ° C. 100% RH).
H), and the unit of the laminate intensity is (gf /
15 mm width). In Table 1 above, the oxygen permeability of Example 3 relating to the barrier film was 0% R
H is the measurement result under the condition of H, and the oxygen permeability and the water vapor permeability of Example 3 and Comparative Example 3 relating to the laminated material.
The laminate strength is a measurement result of the laminated material after the retort treatment.

As is clear from Table 1 above, Example 1
Each of the laminates according to Comparative Examples 1 to 4 has an oxygen barrier property, a water vapor barrier property, and a laminating property as compared with the laminates according to Comparative Examples 1 to 3.
The strength was excellent.

[0046]

As is apparent from the above description, the present invention uses a physical vapor deposition apparatus on one surface of a substrate film and adjusts the degree of vacuum in a deposition chamber to 1.0 to 10%. ^-3
mbar ~ 1.0 × 10 ^-2 mbar to prepare a barrier film by providing a deposited film of aluminum oxide to produce a barrier film, the deposited film of aluminum oxide formed on one surface of the base film, A vapor-deposited film having low crystallinity and being more amorphous can be formed, and the film hardness also decreases. For example, when the film is wound on a take-up roll after the vapor deposition, a guide roll immediately after the vapor deposition, etc. Contact with, or
Prevents the occurrence of microcracks and the like in contact with the take-up roll, etc., and further uses the produced barrier film, and performs printing, laminating, bag making,
Even after other post-processing, etc., generation of cracks or the like is not observed in the deposited film of aluminum oxide, and a laminated material having an extremely high barrier property against oxygen gas or water vapor can be produced. As the above-mentioned deposited film of aluminum oxide, since a deposited film having a small residual stress can be formed, it has heat resistance and, for example, the content was packed and packaged using a packaging bag using the above laminated material. Even if the semi-packaged body is subjected to a high-temperature treatment such as retort, the resulting volume change (thermal shrinkage) is small, and the accompanying deterioration in barrier properties can be minimized.
A barrier film useful for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, electronic parts, and the like, and a laminated material using the same can be produced.

[Brief description of the drawings]

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

FIG. 2 is a schematic cross-sectional view showing a layer configuration of an example of a laminate according to the present invention manufactured using the barrier film according to the present invention shown in FIG.

FIG. 3 is a schematic configuration diagram showing a configuration of a take-up type vacuum evaporation apparatus.

[Explanation of symbols]

 Reference Signs List A barrier film B laminated material 1 base film 2 inorganic oxide deposited film 3 heat-sealing resin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) C08L 67:00 C08L 67:00 77:00 77:00 F term (reference) 4F006 AA35 AB73 AB74 BA05 CA07 DA01 4F071 AA46 AF07 AH04 BC01 4F100 AA17B AA19B AK01A AK01C AK06 AK42 AK51G BA02 BA03 BA04 BA05 BA07 BA10A BA10C CB02 EH66B EJ55 EJ59B EJ65 GB17 GB23 GB41 GB66 JD02 JD03 JD04 JJ03 JK14 A12B03A12B12A12

Claims (4)

[Claims] 1. A physical vapor deposition apparatus is used on one surface of a substrate film, and the degree of vacuum in the deposition chamber is set to 1.
Barrier film, characterized in that to adjust the range of 0~10 ^-3 mbar~1.0 × 10 ^-2 mbar providing a deposited film of an inorganic oxide. 2. The barrier film according to claim 1, wherein the physical vapor deposition apparatus comprises an electron beam heating reaction type physical vapor deposition apparatus. 3. The method according to claim 1, wherein the inorganic oxide vapor-deposited film comprises an aluminum oxide vapor-deposited film.
3. The barrier film according to 2. 4. A physical vapor deposition apparatus is used on one surface of a substrate film, and the degree of vacuum in the deposition chamber is set to 1.
The surface of the deposited film of the inorganic oxide of the barrier film consisting adjusted provided the deposited film of the inorganic oxide structure in the range of 0~10 ^-3 mbar~1.0 × 10 ^-2 mbar, at least, human -A laminated material comprising a sealing resin layer.