JP2001322201A - Barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film excellent in transparency and the barrier properties against oxygen gas, steam or the like, having good adhesiveness and excellent laminating properties, excellent in processability such as printability, laminating processability, bag making processability or other post- treatment processability and useful for packaging food and drink, medicines, cosmetics, chemical products, electronic parts or various other articles and a laminated material using the same. SOLUTION: The barrier film is constituted by providing a first plasma treatment surface on one surface of a base material film, and providing a vapor deposition film comprising a metal or a metal oxide on the first plasma treatment surface while providing a second plasma treatment surface on the other surface of the base material film. The laminated material using this film is also 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. It has excellent adhesiveness and excellent laminating suitability, and has excellent suitability for post-processing such as printing, laminating, bag making, etc., for example, food and drink, pharmaceuticals, cosmetics It is an object of the present invention to provide a barrier film useful for filling and packaging various articles such as chemicals, electronic parts, 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 for preventing permeation of oxygen gas or water vapor, an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like is used on the surface of a plastic substrate, and is subjected to vacuum deposition, sputtering, ion plating, or the like. Physical vapor deposition (PVD), such as the plating method, or chemical vapor deposition (CVD), such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. Accordingly, a transparent gas barrier film formed by forming a vapor-deposited film of the inorganic oxide has attracted attention. Thus, the above-mentioned transparent gas barrier film, on one side, or on both sides, laminated another plastic film, paper base, etc. to produce a laminated material, further using the laminated material, This is made into a bag or box to produce packaging containers of various forms, and thereafter, in the packaging container, for example, food and drink, pharmaceuticals, cosmetics, and other various articles such as filling and packaging. They manufacture packaging products and supply them to the market.
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, the transparent gas barrier film as described above has a plastic substrate on one side and a vapor-deposited inorganic oxide film on the other side. When a desired printed pattern is provided on the surface of the plastic substrate, or when another plastic film or the like is laminated, the surface of the plastic substrate has a low surface tension and poor wettability. A printing process for forming a desired print pattern, or a lamination process for laminating other plastic films, etc.
This makes other operations and operations extremely difficult. For this reason, in the above-mentioned transparent gas barrier film, usually, a primer agent layer is provided on the surface of the inorganic oxide vapor-deposited film, and a printed pattern or the like is formed thereon. A heat-sealing resin layer or the like is dry-laminated via a layer or the like to produce a laminated material as a packaging material. However, also in this case, the vapor deposition film of the inorganic oxide has poor flexibility and the like, and is glassy, so that the primer agent layer,
When forming printed patterns, adhesive layers for dry lamination, laminated materials, etc., winding, coating, printing, laminating, or bag making of the transparent barrier film, etc. In such post-processing, 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, water vapor, and the like is significantly reduced.

Incidentally, for example, a deep-drawing laminated material for filling and packaging ham, sausage and the like, or a laminating material for a liquid pouch filled and packaged with soy sauce, sauce and the like is used as a barrier material. When the above transparent gas barrier film is used, at least a substrate printed on the front side, the above transparent gas barrier film, and a heat-sealing resin layer are sequentially laminated to produce a laminated material. It is necessary to use the above-mentioned transparent gas barrier film for so-called middle use. Further, when filling and packaging contents such as sprinkles, use a base film into which an antistatic agent or the like has been kneaded and processed as a base film, and on one surface thereof, a vapor-deposited film of an inorganic oxide or the like. To form a laminated material by providing a heat-sealing resin layer or the like on the surface of the inorganic oxide vapor-deposited film, and then form a soft packaging bag using the laminated material. Attempts have been made to fill and package the contents such as sprinkles, but in this case, it is necessary to deposit an inorganic oxide vapor deposited film on the base film itself kneaded with an antistatic agent and the like. Is extremely difficult. For this reason, in the laminated material for a soft packaging bag that fills and packs contents such as sprinkles, as described above, when the transparent gas barrier film is used, at least, the front-printed base film and the transparent A gas barrier film and a heat-sealing resin layer must be sequentially laminated to produce a laminated material, and it is necessary to use the above-mentioned transparent gas barrier film for so-called mid-use applications. There is something.
However, when the above-mentioned transparent gas barrier film is used for so-called middle use, as described above, the surface tension of the plastic substrate is low, the wettability is poor, and the inorganic oxide vapor-deposited film Have problems such as generation of cracks. Therefore, the present invention provides transparency,
Excellent barrier properties against oxygen gas or water vapor, etc.
Furthermore, it has good adhesiveness, excellent laminating suitability, and excellent suitability for post-processing such as printing, laminating, bag making, etc. ,
An object of the present invention is to provide a barrier film useful for filling and packaging various articles such as pharmaceuticals, cosmetics, chemicals, electronic parts, and others, and a laminated material using the same.

[0005]

As a result of various studies to solve the above problems, the present inventor has found that immediately before forming a metal or metal oxide deposited film on one surface of a substrate film. Forming a first plasma-treated surface by plasma discharge treatment, and then forming a metal or metal oxide deposited film on the first plasma-treated surface; On the surface of the second by plasma discharge treatment
When the barrier film was manufactured by forming the plasma-treated surface of the above, the other surface of the base film had the second plasma-treated surface, so that the surface tension was strong, the wettability was excellent, and the like was extremely good. It has adhesiveness and excellent laminating suitability with other plastic films, etc. On the other hand, on one surface of the above-mentioned base film, a dense inorganic oxide of Can form a deposited film,
In addition, compared to conventional products, it has a sufficiently high barrier property even at a thinner film thickness, and has excellent adhesion between the surface of the base film and the deposited film of inorganic oxide, and has a printing process and a laminating process. No cracks are found in the metal or metal oxide deposited film during post-processing such as bag making, etc., and it has an extremely high barrier property against oxygen gas or water vapor, and has excellent transparency For example, the present invention has been found that a barrier film useful for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, electronic components, etc. and a laminate using the same can be produced. It is completed.

That is, according to the present invention, a first plasma treatment surface is provided on one surface of a base film, and a metal or metal oxide deposited film is provided on the first plasma treatment surface. On the other hand, on the other surface of the base film, a second
And a laminated material using the same.

[0007]

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 is provided with a first plasma processing surface 2 on one surface of a base film 1, and further comprises a first plasma processing surface 2. A metal or metal oxide deposited film 3 is provided on the
On the other hand, the basic structure is such that the second plasma processing surface 4 is provided on the other surface of the base film 1. Thus, in the present invention, as the laminated material B using the above-mentioned barrier film A according to the present invention, as shown in FIG. 2, the second layer constituting the above-mentioned barrier film A shown in FIG. The basic structure is such that at least resin films 5 and 5a are laminated on both surfaces of the plasma processing surface 4 and the surface of the metal or metal oxide deposited film 3. The above examples are only examples of the barrier film, the laminated material, and the like according to the present invention, 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, the production method thereof, and the like will be described. The constituent base film is excellent in chemical or physical strength, withstands the conditions for plasma treatment described below, or the conditions for forming a metal or metal oxide vapor deposition film, etc. The substrate can be favorably retained without impairing the properties of the deposited film and the like, and a substrate can be used.
In the present invention, as the base film, specifically, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, acrylonitrile-
Styrene copolymer (AS resin), acrylonitrile-
Butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide such as various nylons Films or sheets of various resins such as a resin, a polyurethane resin, a fluorine resin, an acetal resin, a cellulose resin, and others can be used. In the present invention, among the above resin films or sheets, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

[0010] 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 an extrusion method, a cast molding method, a T-die method, a cutting method, or the like. 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.

When one or more of the above various resins are used and the film is formed, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability,
For the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc., various plastic additives and additives can be added. Can,
The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
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 first plasma processing surface and the second plasma processing surface constituting the barrier film, the laminated material and the like according to the present invention will be described. And the second plasma treatment surface is formed on both surfaces by using a plasma surface treatment method for performing surface modification using a plasma gas generated by ionizing a gas by glow discharge. It 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, and the first plasma treatment surface, In addition, a second plasma processing surface can be formed. Thus, in the present invention, the plasma treatment performed on the surface of the base film includes:
At the time of the plasma discharge treatment, it is preferable to perform the plasma treatment using an oxygen gas or a mixed gas of an oxygen gas and an argon gas. With such a plasma treatment, it is possible to perform the plasma treatment at a lower voltage. It is possible to prevent discoloration or the like of the surface of the base film, and to provide the first plasma-treated surface and the second plasma-treated surface satisfactorily on the surface. .

In the present invention, in the above-mentioned plasma treatment, an oxygen gas or a mixed gas of an oxygen gas and an argon gas is particularly used. It is desirable to perform in-line immediately before or immediately after the formation of a vapor deposition film. That is, in the present invention, according to a first example, a base film is mounted on, for example, a supply roll in a roll-up type vacuum evaporation apparatus, and one surface of the base film is coated with metal. Or, immediately before forming a metal oxide deposited film, by performing in-line plasma treatment, while removing moisture and dust and the like attached to the surface of the substrate film, further activated in the plasma Oxygen molecules and the like cause a chemical reaction with the surface of the base film to provide a thin and highly smooth oxide film on the treated surface or a first plasma treated surface on which a hydroxyl group (-OH group) or the like is formed. Is what you can do. Thus, in the present invention, an oxide film or a hydroxyl group (−) is formed on one surface of the base film by the plasma treatment as described above.
On the first plasma-treated surface on which the OH group or the like is formed, a vapor-deposited film of a metal or a metal oxide is formed in-line by vapor deposition as described below, and on the other hand, the other surface of the base film, Immediately after forming the above-mentioned metal or metal oxide vapor-deposited film on the surface of the non-metal or metal oxide vapor-deposited film, plasma processing is performed in-line in the same manner as described above, and the second plasma-treated surface is formed. It can be formed to produce the barrier film according to the present invention.

In the present invention, as a second example, a base film is mounted on, for example, a supply roll in a roll-up type vacuum evaporation apparatus, and both surfaces of the base film are mounted. Immediately before forming a metal or metal oxide deposited film, by performing plasma treatment on both surfaces in-line, moisture and dust attached to the surface of the base film are removed, Oxygen molecules and the like activated in step 1 cause a chemical reaction with the surface of the substrate film, thereby forming a thin and highly smooth oxide film or a hydroxyl group (-OH group) or the like on the treated surface. A plasma processing surface and a second plasma processing surface can be provided. Thus, in the present invention, an oxide film is formed on one surface of the base film by the plasma treatment as described above,
Alternatively, the first group in which a hydroxyl group (—OH group) or the like is formed
On the plasma treated surface, by vapor deposition as described below, to form a metal or metal oxide deposited film in-line,
The barrier film according to the present invention can be produced. The above exemplifications illustrate just a couple of examples, and it is needless to say that the present invention is not limited to these.

According to the present invention, the first plasma-treated surface having an oxide film or a hydroxyl group (—OH group) formed on the surface of the substrate film by the above-described plasma treatment. When a metal or metal oxide deposited film is formed in-line by vapor deposition as described later, a very dense metal or inorganic oxide deposited film is formed without intervening impurities such as impurities. In addition, it is possible to form a thin film having a sufficiently high barrier property against oxygen gas or water vapor with a small thickness. Moreover, in the present invention, the metal or metal oxide deposited film can be formed with a smaller film thickness as described above, and can be sufficiently formed as a high-barrier thin film against oxygen gas or water vapor. 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-mentioned metal or metal oxide deposited film. It also has the advantage that the suitability for post-processing can be improved. Further, in the present invention, as described above, because the excellent adhesion between the base film and the metal or metal oxide deposited film is excellent,
It also improves the suitability for laminating a film or sheet of another resin. In addition, in the present invention, the plasma treatment is performed in-line immediately before the formation of a metal or metal oxide deposited film on the surface of the base film, so that the production cost of the barrier film is also compared with other methods. It is extremely excellent. On the other hand, in the barrier film according to the present invention, since the other surface of the substrate film has a plasma-treated surface, its surface tension is strong, excellent in wettability, etc., and has extremely good adhesion,
When laminated with another plastic film or the like, a laminate material having excellent laminating suitability and extremely useful as a packaging material can be produced.

In the present invention, in the above-mentioned 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, a method for generating plasma in the plasma processing includes, for example, a DC glow discharge and a high frequency (Audio Frequency).
ency: AF, Radio Frequency: R
F) It can be performed using three types of devices such as discharge and microwave discharge.

In the present invention, the plasma-treated surface formed by the above-described plasma treatment on the surface of the base film immediately before or immediately after the formation of the metal or metal oxide deposited film is described in VG Science, UK. X-ray photoelectron spectroscopy analyzer (model name, XP
By performing elemental analysis of the treated surface using S), as described above, moisture and dust attached to the surface of the base film were removed, and furthermore, activated in the plasma. Oxygen molecules cause a chemical reaction with the surface of the substrate film to form a thin and highly smooth oxide film on the surface to be treated. Further, the surface of the substrate film has, for example, a hydroxyl group. It is possible to confirm that the surface is a plasma-treated surface on which a functional group such as (-OH group) is formed. Specifically, as an X-ray source,
XPS analysis of the surface to 100 ° was performed under the measurement conditions of MgKα1.2, X-ray output of 15 Kv, and 20 mA, and the formation state of the oxide film was determined by measuring the composition ratio of O / C (oxygen and carbon) on the surface. to can see, also, the state of formation of such hydroxyl group (-OH group) is of O1 _S 532 eV
The peak obtained at the position can be confirmed by measuring.

Next, in the present invention, the metal or metal oxide deposited film constituting the barrier film, the laminated material and the like according to the present invention will be described. Specifically, any thin film in which a metal or an oxide of the metal is made amorphous can be used. For example, silicon (Si),
Aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (P
b) a metal such as zirconium (Zr) or yttrium (Y) or an oxide of the metal as an amorphous
A thin film can be used. Thus, as a material suitable for a packaging material or the like, a metal such as aluminum (Al), or silicon (Si) or aluminum (A
Examples of the thin film include an oxide of a metal such as 1) made amorphous. A thin film in which the above metal oxide is made amorphous can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, magnesium oxide, and the like.
MO _X (however, such as O _X , AlO _X , MgO _X, etc.)
In the formula, 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 metal or metal oxide deposited film varies depending on the type of the metal or metal oxide to be used.
It is desirable to arbitrarily select and form it in the range of about 0 to 2000 °, preferably about 100 to 1000 °. More specifically, in the case of an aluminum vapor-deposited film, the film thickness is about 50 to 600 °, more preferably 100 to 600 °.
In the case of a deposited film of aluminum oxide or silicon oxide, the thickness is preferably 50 to 500 °.
And 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 or the like are generated in the deposited film of the metal or metal oxide, and the barrier properties against oxygen gas, water vapor, etc. are remarkably reduced.
It is not preferable because the close adhesion to the base film decreases. Further, in the present invention, the deposited film of the metal oxide is not limited to one layer of the deposited film of the metal oxide, but may be a laminate of two or more layers. Alternatively, as the metal oxide, one kind or a mixture of two or more kinds can be used to form a vapor-deposited film of a metal oxide mixed with different materials.

Next, in the present invention, a method for forming a metal or inorganic oxide deposited film on the first plasma treated surface of the base film will be described. Physical vapor deposition methods (Physic, such as sputtering, ion plating, etc.)
al Vapor 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.
medical Vapor Deposition method, C
VD method). In the present invention, the method for forming a metal or metal oxide deposited film will be specifically described. First, a metal or metal oxide as described above is used as a raw material, which is heated to perform first plasma treatment of a base film. Vacuum evaporation method of vapor deposition on the surface, or oxidation using a metal or metal oxide as a raw material, introducing oxygen gas or the like and oxidizing to vapor-deposit on the first plasma treatment surface of the base film The deposited film can be formed by a reactive vapor deposition method, or a plasma-assisted oxidation reaction vapor deposition method in which an oxidation reaction is promoted by plasma. 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 method for forming a metal or metal oxide vapor deposition film will be described with reference to a specific example. FIG. 3 is a schematic configuration diagram showing an example of a roll-up type vacuum vapor deposition apparatus. As shown in FIG. 3, first, the base film 1 is unwound from the unwinding roll 13 in a vacuum chamber 12 constituting the winding type vacuum evaporation apparatus 11, and the base film 1 is -Ting drum 14
, And transferred into the deposition chamber 15. Thus, in the present invention, immediately before the base film 1 is transferred into the vapor deposition chamber 15, a plasma processing apparatus 20 is provided as a pre-processing unit, and the plasma processing apparatus 20 One surface of the material film 1 is sufficiently subjected to plasma processing to form a first plasma processing surface,
Next, the base film 1 is transported into the deposition chamber 15. On the other hand, in the evaporation chamber 15, the evaporation source (for example, 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 blowout port 17. The metal or metal oxide is deposited via the masks 18 on the first plasma-treated surface of the base film 1 on the cooled coating drum 14 introduced into the deposition chamber 15 above. A film is formed, and then the substrate film 1 on which a metal or metal oxide vapor-deposited film is formed is fed into the vacuum chamber 12. Thus, in the present invention, immediately before the base film 1 is taken up by the take-up roll 19, a plasma processing apparatus 20a is provided as a pre-processing unit, and the plasma processing apparatus 20a uses the plasma processing apparatus 20a. On the other surface of the base film 1 provided with the first plasma treatment surface and the metal or metal oxide deposited film on one surface, a sufficient plasma treatment is performed to form a second plasma treatment surface, Roll up the base film 1
By winding the film into No. 9, the barrier film according to the present invention can be manufactured.

In the example shown in FIG. 3, instead of forming the first plasma processing surface by the plasma processing device 20 and the second plasma processing surface by the plasma processing device 20a, the base film 1 is deposited. Chamber-15
Immediately before being conveyed into the apparatus, a plasma processing apparatus 20 and a plasma processing apparatus 20b are provided as a pre-processing unit. To form a first plasma-treated surface and a second plasma-treated surface, and then transport the substrate film 1 into the vapor deposition chamber 15, and thereafter, in the same manner as described above. Then, the evaporation source (for example, aluminum or aluminum oxide) heated in the crucible 16 is evaporated.
If necessary, the base film 1 on the cooled coating drum 14 conveyed into the vapor deposition chamber 15 while blowing oxygen gas or the like from the oxygen blowing port 17.
A metal or metal oxide deposited film is formed on the first plasma processing surface through the masks 18, 18 to form a metal or metal oxide deposited film; The barrier film according to the present invention is manufactured by feeding the substrate film 1 on which the oxide vapor-deposited film is formed into the vacuum chamber 12 and then winding the substrate film 1 around the winding roll 19. can do.

Further, in the present invention, a specific example of the above-mentioned 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 the base film 1 at a constant speed from the roll 23 through an auxiliary roll 24 or the like, the base film 1 is conveyed onto the cooling / electrode drum 25 peripheral surface. Thus, in the present invention, immediately before the base film 1 is conveyed on the peripheral surface of the cooling / electrode drum 25, a plasma processing device 34 is provided as a pre-processing unit. Then, one surface of the base film 1 is sufficiently subjected to plasma processing to form a first plasma-treated surface, and then the base film 1 is conveyed onto the cooling / electrode drum 25 peripheral surface. Next, the substrate film 1 is conveyed onto the peripheral surface of the cooling / electrode drum 25 and, for example, an organic silicon compound as a vaporized monomer gas and an oxygen gas supplied from the raw material volatile supply devices 26, 27 and 28. , An inert gas, and other mixed gas through a material supply nozzle 29 through a vacuum chamber 22
The glow discharge plasma 30 is used to form a metal oxide deposited film such as a silicon oxide deposited film on the first plasma treated surface of the base film 1. I do. Next, in the present invention, immediately before the base film 1 is wound around the winding roll 33 via the auxiliary roll 24 or the like, the plasma processing apparatus 34 is used as a pretreatment unit.
The first plasma processing surface and the other surface of the base film 1 on which a metal or metal oxide vapor-deposited film is provided on one surface are sufficiently subjected to plasma processing by the plasma processing apparatus 34a. To form a second plasma-treated surface, and then take up the base film 1 on a take-up roll 33 via an auxiliary roll 24 or the like to produce a barrier film according to the present invention. can do. At this time, a predetermined voltage is applied to the cooling / electrode drum 25 from a power supply 31 disposed outside the vacuum chamber 22. A magnet 32 is provided near the cooling / electrode drum 25. Arrangement promotes generation of plasma, and prepares a deposited film of a metal oxide such as a deposited film of silicon oxide. In the drawing, reference numeral 33 denotes a vacuum pump.

In the example shown in FIG. 4, instead of forming the first plasma processing surface by the plasma processing device 34 and the second plasma processing surface by the plasma processing device 34a, the base film 1 is cooled.・ Electrode drum 2
Immediately before being conveyed on five circumferential surfaces, as a pre-processing unit,
Plasma processing device 34 and plasma processing device 34
The first plasma processing surface and the second plasma processing surface are formed by simultaneously performing sufficient plasma processing on both surfaces of the base film 1 by the plasma processing devices 34 and 34b. Then, the substrate film 1 is conveyed onto the peripheral surface of the cooling / electrode drum 25, and thereafter supplied in the same manner as described above from the raw material volatilizing supply devices 26, 27, 28, for example, a vaporized monomer gas. A mixed gas comprising an organic silicon compound, oxygen gas, inert gas, and the like as a gas is supplied through a material supply nozzle 29 to a vacuum chamber 22.
Then, a deposited film of a metal oxide such as a deposited film of silicon oxide is formed on the first plasma-treated surface of the base film 1 by the glow discharge plasma 30. Thereafter, the base film 1 on which the metal or metal oxide vapor-deposited film is formed is wound up on the take-up roll 33 via an auxiliary roll or the like, whereby the barrier according to the present invention is obtained. Film can be produced.
The examples illustrated in FIGS. 3 and 4 above illustrate a few examples of manufacturing the barrier film according to the present invention,
The present invention is not limited by this. In the present invention, for example, although not shown, instead of forming a plasma processing surface, a metal or metal oxide deposited film or the like in-line as illustrated in FIGS. Forming a surface, and then forming a metal or metal oxide deposited film or the like using a roll-up vacuum deposition device, or a plasma chemical vapor deposition device, etc. A film can be manufactured.

In the above, the thin film mainly composed of a silicon oxide vapor deposition film as a metal oxide vapor deposition film is composed of a silicon compound having at least silicon and oxygen as constituent elements, and further has carbon or carbon as a trace constituent element. It contains one or more elements of hydrogen and has a thickness of 50 to 500 Å
And more preferably in the range of about 100-300 °. Thus, in the present invention, as the silicon oxide thin film as described above, an organic silicon compound is used as a raw material, and a vapor-deposited film formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like is used. be able to. In the above, as the organic silicon compound, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane,
Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, 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. To get
It is desirable to use a generator using a high-frequency plasma method.

In the present invention, among the above-mentioned metal or metal oxide vapor-deposited films, aluminum or aluminum oxide formed by physical vapor deposition using the above-mentioned roll-up type vacuum vapor deposition apparatus or the like is used. The vapor-deposited film effectively interacts with the plasma-treated surface to be described later, effectively exhibiting a synergistic effect of both, and a barrier in which the base film and the metal or metal oxide vapor-deposited film are firmly and closely adhered. It can produce a functional film. In particular, in the present invention, as described above, immediately before the deposition of a metal or metal oxide deposition film in-line, a plasma treatment is performed to form a plasma-treated surface, and the base film and the metal or metal oxide deposition This improves the tight adhesion with the film.

Next, in the present invention, a resin film and the like constituting a laminated material manufactured using the barrier film according to the present invention will be described. As the resin film and the like, various types are used. For example, first, a heat-sealing resin film or sheet constituting the heat-sealing resin layer can be used. Thus, the heat-sealing resin film or sheet constituting the heat-sealing resin layer is usually formed of a heat-sealing resin film or sheet.
It is laminated on the surface of the metal or metal oxide vapor deposition film of the barrier film according to the present invention. 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-based adhesive, ethyl, butyl, 2-ethylhexyl ester of acrylic acid. And the like, or a homopolymer such as 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, in particular, a one-component adhesive containing a polyurethane-based compound obtained by reacting a di- or polyisocyanate compound with a di- or polyoxy compound as a main component. 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 or the like in the deposited film of metal or metal oxide during post-processing.

In the present invention, the adhesive layer for dry laminating may be formed using 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 improves the close adhesion with the metal or metal oxide deposited film constituting the laminate, the printed pattern layer, and the like, whereby the metal or metal oxide is formed. This prevents cracks and the like from occurring in the deposited film. In the above, if the tensile elongation is less than 300%, it lacks flexibility,
In post-processing such as bag making or box making, cracks and the like are generated in the metal or metal oxide deposited film, and when the tensile elongation exceeds 550%,
It is not preferable because the flexibility is excessive and the tearing property is poor, for example, the openability of the packaging container is poor. 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 laminated material 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 laminate 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 and 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. A material that satisfies the above conditions can be arbitrarily selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
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-described 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 thereof, and the heat-sealing resin layer is folded, or the two sheets are overlapped, and the peripheral end is further folded. 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 the 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 brick-type, flat-type or gable-top type liquid paper container. 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, the packaging containers produced as described above include various 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.

[0042]

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
An axially stretched polyethylene terephthalate film is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then,
One surface of the biaxially stretched polyethylene terephthalate film was subjected to plasma treatment in-line using a discharge plasma generator under the following conditions to form a first 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: surface to be deposited After forming the first plasma-treated surface, the first plasma-treated surface was formed by a vacuum evaporation method using an electron beam (EB) heating method using aluminum as an evaporation source under the following evaporation conditions. 400
An aluminum vapor-deposited film was formed. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface : Plasma-treated surface Further, on the other surface of the biaxially stretched polyethylene terephthalate film on which the first plasma-treated surface and the aluminum vapor-deposited film were formed, a discharge plasma generator was used in-line in the same manner as described above. Then, a plasma treatment was performed under the following conditions to form a second plasma treatment surface, and a barrier film according to the present invention was manufactured. (Plasma processing conditions) Glow-discharge gas: Argon Power supply: DC Discharge power: 30 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma-treated surface: non-deposited surface For the plasma treated surface, the static friction coefficient and the dynamic friction coefficient were measured using a slip tester (model TR-2) manufactured by Toyo Seiki Seisaku-sho, Ltd.
0.63 μ, coefficient of kinetic friction, 0.57 μ. (2). Next, a primer composition (manufactured by The Inktec Co., Ltd.) was used to coat the aluminum film of the barrier film produced above by a gravure roll coating method to obtain a film thickness. A primer layer of 0.02 g / m ² (dry state) is formed, and a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., on the surface of the primer layer) Name, Takerack A-515 / Takenate A-12), coated by a gravure roll coating method to obtain an adhesive for dry laminate having a thickness of 4.0 g / m ² (dry state). A layer was formed, and then a 20 μm-thick biaxially oriented polypropylene film having a desired printed pattern was dry-laminated on the surface of the adhesive layer for dry laminating with the printed pattern faced. On the other hand, a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name) is applied to the second plasma-treated surface of the biaxially stretched polyethylene terephthalate film of the barrier film produced above. , Bamboo Rack A-515 / Bamboo
A-12), and coated by a gravure roll coating method to obtain a film thickness of 4.0 g / m ² (dry state).
Then, a 30 μm-thick linear low-density polyethylene film was dry-laminated on the surface of the dry-laminate adhesive layer to produce a laminate according to the present invention. . A three-sided seal-type soft packaging bag was manufactured using the above laminated material,
As a result of filling and packaging frozen foods such as towels to produce a packaged product, the product was able to withstand distribution, storage, sale and the like in the market.

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. First, 2
An axially stretched polyethylene terephthalate film is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then,
One surface of the biaxially stretched polyethylene terephthalate film was subjected to plasma treatment in-line using a discharge plasma generator under the following conditions to form a first 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: surface to be deposited Next, in-line After forming the first plasma-treated surface, the first plasma-treated surface was supplied with oxygen gas using aluminum as a vapor deposition source, and was then irradiated with an electron beam (E).
B) A 200-nm-thick aluminum oxide vapor-deposited film was formed by a reactive vacuum vapor deposition method using a heating method under the following vapor deposition conditions. (Deposition conditions) Degree of vacuum in deposition chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 35 kW Film transport speed: 480 m / min Deposition surface : Plasma-treated surface Further, a biaxially stretched polyethylene terephthalate on which a first plasma-treated surface and a deposited film of aluminum oxide are formed as described above.
In the same manner as described above, a plasma treatment is performed on the other surface of the film using an in-line discharge plasma generator under the following conditions to form a second plasma treatment surface, and the barrier film according to the present invention is formed. Was manufactured. (Plasma processing conditions) Glow-discharge gas: Argon Power supply: DC Discharge power: 30 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma-treated surface: non-deposited surface For the plasma treated surface, the static friction coefficient and the dynamic friction coefficient were measured using a slip tester (model TR-2) manufactured by Toyo Seiki Seisaku-sho, Ltd.
0.63 μ, coefficient of kinetic friction, 0.57 μ. (2). Next, a primer composition (manufactured by The Inktec Co., Ltd.) was used to coat a gravure roll on the aluminum oxide vapor-deposited film surface of the barrier film produced above.
Coating by the coating method to a film thickness of 0.02 g / m
^{2 A} (dry) primer layer is formed, and a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name,
Using Takerack A-515 / Takenate A-12), coating by gravure roll coating method,
An adhesive layer for dry lamination having a thickness of 4.0 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 laminate. On the other hand, a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name) is applied to the second plasma-treated surface of the biaxially stretched polyethylene terephthalate film of the barrier film produced above. , Bamboo Rack A-515 / Bamboo Net
A-12) was coated by a gravure roll coating method to form a dry laminating adhesive layer having a thickness of 4.0 g / m ² (dry state). A 20 μm-thick biaxially stretched polypropylene film was dry-laminated on the surface of the adhesive layer for a laminate, to produce a laminate according to the present invention. In addition, using the above-mentioned laminated material, a three-sided seal-type flexible packaging bag was manufactured, and a packed product was manufactured by filling and packaging frozen food such as a meatball. It was able to withstand storage and sale.

Embodiment 3 (1). Use a rewind-type vacuum evaporation system and
As a material film, biaxially stretched nylon 6 having a thickness of 15 μm
Film was used. First, the above biaxially stretched nylon 6
Rolling out roll of vacuum evaporator for winding film
And then one of the biaxially stretched nylon 6 films
On the surface, using an in-line discharge plasma generator,
The plasma processing is performed under the following conditions, and the first plasma processing is performed.
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: the surface to be deposited, then the first plasma of a biaxially stretched nylon 6 film
On the treated surface, use aluminum as the evaporation source to
Electron beam (EB) heating method while supplying
By the vacuum deposition method according to the formula, the film is deposited under the following deposition conditions.
An aluminum oxide deposited film having a thickness of 200 ° was formed. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10^-Fourmbar The degree of vacuum in the take-up chamber: 2 × 10^-2mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface: plasma treated surface Further, the first plasma treated surface and aluminum oxide
The other of the biaxially stretched nylon 6 films on which the deposited film of
In-line discharge plasma in the same manner as above
Using a generator, perform plasma processing under the following conditions,
A second plasma processing surface is formed to form a burr according to the present invention.
A film was manufactured. (Plasma treatment conditions) Glow discharge gas: Argon Power supply: DC Discharge power: 30 W · min / m^Two Glow discharge pressure: 2.0 × 10^-2mbar Plasma-treated surface: non-deposited surface The above-mentioned second plasma-treated surface is referred to as Toyo Seiki
Using a slip tester (Model TR-2) manufactured by Seisakusho Co., Ltd.
As a result of measuring the static friction coefficient and the dynamic friction coefficient, the static friction coefficient,
The coefficient of dynamic friction was 0.50μ, and the coefficient of dynamic friction was 0.45μ. (2). Next, oxidation of the barrier film produced above
The primer composition (The i
Using the product name PD-4) manufactured by NuncTech Co., Ltd.
Coating by gravure roll coating, film thickness
0.02 g / m ^TwoFormation of (dry) primer layer
Then, a two-component curing type polymer is applied to the surface of the primer layer.
Adhesive for urethane dry laminate (Takeda Pharmaceutical Co., Ltd.
Company name, product name, bamboo rack A-515 / bamboo
 A-50) by the gravure roll coating method
Coated to a film thickness of 4.0 g / m^Two(Dry)
Forming an adhesive layer for dry lamination,
A 50 μm thick low-density polymer
The ethylene film was dry-laminated. On the other hand
Biaxially stretched nylon 6 film of the barrier film produced in
A two-component curing type polyurethane is applied to the second plasma-treated surface of the film.
Adhesive for urethane dry laminate (Takeda Pharmaceutical Co., Ltd.
Company name, product name, bamboo rack A-515 / bamboo
 A-12) by the gravure roll coating method
Coated to a film thickness of 4.0 g / m^Two(Dry)
Forming an adhesive layer for dry lamination,
Biaxial stretching with a thickness of 20 μm on the surface of the adhesive layer for illuminating
Dry laminating polypropylene film
A laminate according to the present invention was produced. Note that the above laminated material is used.
To produce a three-sided seal type flexible packaging bag, which contains soy sauce,
As a result of manufacturing packaging products by filling and packaging sources, etc., the market
Can withstand distribution, storage, sales, etc.
Was.

Embodiment 4 (1). A plasma chemical vapor deposition apparatus was used, and a 12 μm-thick biaxially stretched polyethylene terephthalate film was used as a base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and then, on one side of the biaxially stretched polyethylene terephthalate film, an in-line discharge plasma generator is used. Then, plasma treatment was performed under the following conditions to form a first plasma treatment surface. (Plasma treatment conditions) Glow-discharge gas: oxygen gas Power supply: DC Discharge power: 20 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma treatment surface: surface to be deposited On the first plasma-treated surface of the axially stretched polyethylene terephthalate film, a deposited film of silicon oxide having a thickness of 200 mm was formed under the following deposition conditions. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 60 w / min / m ² Film transfer speed: 90 m / min Vapor deposition surface: plasma treated surface Further, the first plasma treated surface and the oxidation The other surface of the biaxially stretched polyethylene terephthalate film on which the silicon deposition film was formed was subjected to plasma treatment in the same manner as above using an in-line discharge plasma generator under the following conditions to obtain a second plasma. The treated surface was formed to produce a barrier film according to the present invention. (Plasma processing conditions) Glow-discharge gas: Argon Power supply: DC Discharge power: 30 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma-treated surface: non-deposited surface For the plasma treated surface, the static friction coefficient and the dynamic friction coefficient were measured using a slip tester (model TR-2) manufactured by Toyo Seiki Seisaku-sho, Ltd.
0.63 μ, coefficient of kinetic friction, 0.57 μ. (2). Next, a primer composition (trade name: PD-4, manufactured by The Inktec Co., Ltd.) was used to coat the silicon oxide vapor-deposited film surface of the barrier film produced above by a gravure roll coating method. -0.02 layer thickness
g / m ² (dry state) of a primer layer.
On the surface of the primer layer, a two-component curable polyurethane dry laminating adhesive (Takelac A-515 / Takenate A-5, product name, manufactured by Takeda Pharmaceutical Co., Ltd.)
0) to form a dry-laminate adhesive layer having a thickness of 4.0 g / m ² (dry state) by coating by a gravure roll coating method. A low-density polyethylene film having a thickness of 50 μm was dry-laminated on the surface of the adhesive layer. On the other hand, a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name) is applied to the second plasma-treated surface of the biaxially stretched polyethylene terephthalate film of the barrier film produced above. , Takeraque A-515 / Takenate A-50) and coated by a gravure roll coating method to obtain a dry laminating adhesive layer having a thickness of 4.0 g / m ² (dry state). Is then formed on the surface of the adhesive layer for dry laminating to a thickness of 20 μm.
Was dried and laminated to produce a laminated material according to the present invention. In addition, using the above-mentioned laminated material, a three-sided seal-type flexible packaging bag was manufactured, and a packed product was manufactured by filling and packaging frozen food such as a meatball. It was able to withstand storage and sale.

Example 5 The barrier film according to the present invention produced in Example 1 was used, and a low-density polyethylene was used on the aluminum film-deposited surface of the barrier film to a thickness of 15 μm. While melt-extruding, an unstretched polypropylene film having a thickness of 20 μm was extruded and laminated.
On the other hand, using a biaxially stretched polypropylene film having a thickness of 20 μm, a low-density polyethylene resin is used on the surface of the corona-treated surface, and while extruding this to a thickness of 15 μm, the barrier extruded and laminated as described above. A laminated material according to the present invention was manufactured by extruding and laminating the biaxially stretched polyethylene terephthalate film of the conductive film with the second plasma-treated surface facing each other, and extruding and laminating both. In addition, using the above-mentioned laminated material, a flexible packaging bag was manufactured in accordance with a conventional method, and cereal such as corn flakes was filled and packaged to manufacture a packaged product. It was able to withstand sales and the like.

Example 6 A low-density polyethylene was used on the aluminum oxide-deposited film surface of the barrier film according to the present invention prepared in Example 2 above, and the thickness was 15 μm. While melt extrusion, an unstretched polypropylene film having a thickness of 20 μm was extruded and laminated. On the other hand, using a biaxially stretched polypropylene film having a thickness of 20 μm, a low-density polyethylene resin is used on the surface of the corona-treated surface, and while extruding this to a thickness of 15 μm, the barrier extruded and laminated as described above. A laminated material according to the present invention was manufactured by extruding and laminating the biaxially stretched polyethylene terephthalate film of the conductive film with the second plasma-treated surface facing each other, and extruding and laminating both. In addition, using the above-mentioned laminated material, a flexible packaging bag was manufactured in accordance with a conventional method, and cereal such as corn flakes was filled and packaged to manufacture a packaged product. It was able to 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 a non-processed surface of an axially stretched polyethylene terephthalate film, aluminum is deposited as a vapor deposition source by a vacuum vapor deposition method using an electron beam (EB) heating method under the following vapor deposition conditions under the following vapor deposition conditions. A film was formed to produce a barrier film. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface : Untreated surface In addition, the other surface (non-deposited film surface) of the base film was measured for a static friction coefficient and a dynamic friction coefficient by a slip tester (Model TR-2) manufactured by Toyo Seiki Seisaku-sho, Ltd. Static friction coefficient, 0.38μ, dynamic friction coefficient, 0.35μ
Met. (2). Next, using the barrier film produced above, hereinafter, in exactly the same manner as in Example 1 above, first, a primer layer is formed on the aluminum deposited film surface of the barrier film produced above, Further, a dry-laminate adhesive layer is formed on the surface of the primer layer, and then a 20 μm-thick biaxially-stretched polypropylene film having a desired print pattern is formed on the dry-laminate adhesive layer surface. Dry lamination was performed with the printed patterns facing each other. On the other hand, on the surface of the biaxially stretched polyethylene terephthalate film of the barrier film produced above, a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, Takerac A-515)
/ Takenate A-12) and coated by a gravure roll coating method to obtain a film thickness of 4.0 g / m2.
² (dry state) An adhesive layer for dry laminate is formed, and then a 30 μm-thick linear low-density polyethylene film is dry-laminated on the surface of the adhesive layer for dry laminate to produce a laminated material. did.

Comparative Example 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. First, 2
An axially stretched polyethylene terephthalate film is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then,
By using aluminum as an evaporation source and supplying oxygen gas to the untreated surface of the biaxially stretched polyethylene terephthalate film, a reactive vacuum evaporation method using an electron beam (EB) heating method was performed under the following evaporation conditions. 200mm thick
Was formed to form a barrier film. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 35 kW Film transport speed: 480 m / min Evaporation surface : Untreated surface In addition, the other surface (non-deposited film surface) of the above substrate film was measured for a static friction coefficient and a dynamic friction coefficient by a slip tester (model TR-2) manufactured by Toyo Seiki Seisaku-sho, Static friction coefficient, 0.38μ, dynamic friction coefficient, 0.35μ
Met. (2). Next, using the barrier film produced above, thereafter, in exactly the same manner as in Example 2 above, a primer layer is formed on the aluminum oxide deposited film surface of the barrier film produced above, Further, an adhesive layer for dry laminating was formed on the surface of the primer layer, and then a low-density polyethylene film having a thickness of 50 μm was dry-laminated on the adhesive layer for dry laminating. On the other hand, on the surface of the biaxially stretched polyethylene terephthalate film of the barrier film produced above, a two-component curable polyurethane-based dry laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., product name, Takelac A-515) / Takenate A-12) 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. ,
On the surface of the dry laminate adhesive layer, a 20 μm thick 2
The laminated material was manufactured by dry laminating the axially stretched polypropylene film.

Comparative Example 3 A 12 μm-thick biaxially stretched polyethylene terephthalate was used as a substrate, using a winding type vacuum evaporation apparatus.
2 using the same film as in Comparative Example 1 above.
On one side of the axially stretched polyethylene terephthalate film,
An aluminum vapor-deposited film having a thickness of 400 ° was formed to produce a barrier film. Next, an unstretched polypropylene film having a thickness of 20 μm was extruded and laminated while using a low-density polyethylene on the vapor-deposited film surface of aluminum of the barrier film produced above and melting and extruding it to a thickness of 15 μm. . On the other hand, using a biaxially stretched polypropylene film having a thickness of 20 μm, a low-density polyethylene resin is used on the surface of the corona-treated surface, and while extruding this to a thickness of 15 μm, the barrier extruded and laminated as described above is used. The biaxially oriented polyethylene terephthalate film of the conductive film was opposed to each other, and both were extruded and laminated to produce a laminated material.

EXPERIMENTAL EXAMPLES Using the barrier films and the laminates produced in the above Examples 1 to 6 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.

[0052] 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 /
The value on the left is the value of the laminate strength on the base film side, and the value on the right is the value of the laminate strength on the metal or metal oxide side.

As apparent from Table 1 above, Example 1
Each of the laminated materials according to Comparative Examples 1 to 6 has an oxygen barrier property, a water vapor barrier property, and a laminating property as compared with the laminated materials according to Comparative Examples 1 to 3.
The strength was excellent.

[0054]

As apparent from the above description, the present invention provides a first plasma treatment by a plasma discharge treatment immediately before forming a metal or metal oxide deposited film on one surface of a base film. Forming a metal or metal oxide vapor-deposited film on the first plasma-treated surface, and applying a second plasma discharge treatment to the other surface of the base film. A plasma treated surface is formed to produce a barrier film, and the other surface of the base film has a second plasma treated surface, so that the surface tension is strong, the wettability, etc. are excellent, and the adhesion is extremely good. And has excellent suitability for lamination with other plastic films, etc. On the other hand, on one surface of the base film, a dense inorganic oxide is deposited via the first plasma treated surface. A film can be formed, and Compared to the original product, it has a sufficiently high barrier property even with a thinner film thickness, and has excellent adhesion between the surface of the base film and the deposited film of inorganic oxide, and has a printing process, a laminating process, No cracks or the like are found in the metal or metal oxide deposited film in post-processing such as bag processing, etc., thereby having an extremely high barrier property against oxygen gas or water vapor, and having a high transparency. Excellent, for example, it is possible to produce a barrier film useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic components, and others, and a laminate using the same. is there.

[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.

FIG. 4 is a schematic configuration diagram showing a configuration of a plasma chemical deposition apparatus.

[Explanation of symbols]

 A Barrier film B Laminated material 1 Base film 2 First plasma treated surface 3 Metal or metal oxide deposited film 4 Second plasma treated surface 5, 5a Resin film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 14/06 C23C 14/06 Q 14/08 14/08 A 14/14 14/14 B 14/24 14 / 24 N // C08L 67:02 C08L 67:02 F term (reference) 4F006 AA35 AA38 AB73 AB74 BA05 CA07 DA01 EA03 4F073 AA17 BA23 BA29 BB01 CA01 4F100 AA19B AB01B AB10B AB17B AK01A AK01C AK01 BA10 BA04A00 BA10 AT04 BA13 EH66B EJ61A GB15 GB23 GB41 GB66 JA20B JD02 JL01 JN01 YY00B 4K029 AA11 BA03 BA44 BA62 BB02 BC02 BD00 CA01 DB03 FA05 GA03 KA07

Claims (7)

[Claims] 1. A first plasma treatment surface is provided on one surface of a substrate film, and a metal or metal oxide vapor-deposited film is further provided on the first plasma treatment surface. A barrier film, wherein a second plasma-treated surface is provided on the other surface of the base film. 2. The method according to claim 1, wherein the first plasma-treated surface is provided in-line on one surface of the base film immediately before providing the metal or metal oxide deposited film. Barrier film. 3. A plasma processing method according to claim 1, wherein the first plasma-treated surface is provided in-line on both surfaces of the base film immediately before the metal or metal oxide deposited film is provided, and a plasma provided on one surface of the base film. The barrier film according to claim 1, comprising a treated surface. 4. The barrier film according to claim 1, wherein the metal or metal oxide deposited film comprises an aluminum or aluminum oxide deposited film. 5. The barrier film according to claim 1, wherein the metal or metal oxide deposited film has a thickness of 100 to 300 °. 6. The method according to claim 1, wherein the second plasma-treated surface is provided in-line after providing a metal or metal oxide deposited film on the other surface of the base film. 2. The barrier film described in 1. 7. A first plasma treatment surface is provided on one surface of a substrate film, and a metal or metal oxide vapor-deposited film is further provided on the first plasma treatment surface. A laminated material characterized in that at least a resin film is laminated on both surfaces of a barrier film having a configuration in which a second plasma-treated surface is provided on the other surface of the base film.