JP2001139193A - Transparent barrier film winding roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent barrier film winding roll preventing the occurrence of blocking of a film roll, easily peeling the film roll at post- processing, preventing the breakage of the film roll and reduction in physical properties and the like of the film roll, having an excellent post-processing property, preventing degradation in a barrier property for preventing the permeation of especially gaseous oxygen and water vapor included in the film roll, and being suitable for filling up and packing various articles including eat and drink articles. SOLUTION: A transparent barrier film roll winds up a roll provided with an inorganic oxide evaporated membrane on one surface of a base film material at least every 2000 to 8000 m in a longitudinal direction while shifting to the right or the left in a width direction by a space not more than 10 mm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rolled-up film of a transparent barrier film, and more particularly, to the prevention of blocking of a rolled-up film in the form of roll-up of the filmed film, which makes it extremely easy to perform post-processing. The film raw material can be peeled off, the film raw material is broken, the physical properties of the film raw material, etc. are prevented from deteriorating, etc., and it has extremely excellent post-processing suitability. The present invention relates to a raw material for winding a transparent barrier film which is useful for filling and packaging various articles such as foods and drinks by preventing deterioration of barrier properties for preventing permeation of water vapor and the like.

[0002]

2. Description of the Related Art Hitherto, laminated materials of various forms and packaging containers using the same have been developed and proposed for filling and packaging various articles such as food and drink. In general, a barrier material for preventing permeation of oxygen gas, water vapor and the like is used in the laminated material, the packaging container and the like in order to prevent the contents from being deteriorated. At present, as a barrier material for preventing permeation of oxygen gas, water vapor and the like, for example, aluminum foil or its vapor-deposited film, or a coating film of polyvinylidene chloride-based resin is generally used. Used. On the other hand, in recent years, as a barrier material for preventing the permeation of the above oxygen gas and water vapor, for example, a chemical vapor deposition method or a physical vapor deposition method is applied to one surface of a base film such as a polyester resin film or a polyamide resin film. A transparent barrier film having a configuration in which a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided using a vapor phase growth method or the like has been developed and proposed. The above-mentioned transparent barrier film is excellent in transparency as compared with a conventional aluminum foil or a vapor-deposited film thereof, or a barrier material composed of a coating film of a polyvinylidene chloride-based resin or the like, and has oxygen, It has high barrier properties against water vapor, etc. and also has various excellent advantages that it does not cause environmental problems at the time of disposal, so it is laminated with other plastic films, paper base materials, cellophane, etc. The demand for such materials as packaging materials is greatly expected.

[0003]

By the way, the above-mentioned transparent barrier film is usually supplied with a base film continuously from a paper feeding roll or the like by using a vacuum evaporation apparatus or the like in which the inside is evacuated. Then, in a vapor deposition chamber, a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is laminated on one side of the base film, and then wound on a take-up roll or the like. In the above, when a film of an inorganic oxide such as silicon oxide or aluminum oxide is laminated and then wound on a winding roll or the like, the films adhere to each other at the winding end of the film. However, there is a problem that a blocking phenomenon is caused. This means that the film must be wound tightly without any gas between the film and the film in order to wind the film in vacuum, and that the film is wound with tension applied. In particular, the blocking phenomenon occurs very easily at the end of the original film due to the strong pressure. By the way, when the blocking phenomenon occurs in the film roll as described above, for example, the film roll wound on the winding roll is peeled off and subjected to post-processing such as slitting to form a small roll. When the film is rolled, the peelability of the film raw material deteriorates, and in some cases, the film must be peeled by applying a certain force to the film. When peeled off, for example, the film raw material breaks, or causes deformation of the film raw material, thereby, made of vitreous, and silicon oxide with poor flexibility,
Cracks and the like are generated in the deposited film of the inorganic oxide such as aluminum oxide, and the barrier performance of preventing the permeation of oxygen gas, water vapor and the like is remarkably deteriorated, and it is difficult to use as a barrier material anymore. There is a problem. Furthermore, even when used as a barrier material as it is, it causes deterioration of the contents, impairs its flavor, taste, etc., and furthermore, there is a problem that storage and preservation stability of the packaged product are inferior,
There is a problem that the value of use as a packaging product is no longer significantly impaired, and it cannot be used as a packaging product. Even if the above-mentioned blocking phenomenon does not occur in the film raw material, the above-mentioned vapor-deposited film of an inorganic oxide such as silicon oxide and aluminum oxide is a vitreous material and is inferior in flexibility. Therefore, when the film material is rolled or bent, cracks and the like are easily generated in the deposited film of the inorganic oxide, so that the film material wound on the winding roll is peeled off. However, it is extremely difficult to increase the line speed when winding up a small roll or the like by performing post-processing such as slit processing, thereby significantly impairing the productivity and reducing the production efficiency. There is a problem that it decreases. Therefore, the present invention prevents the occurrence of blocking of the film raw material in the form of winding of the film raw material, makes it possible to peel off the film raw material very easily during post-processing, breaks the film raw material, It has excellent post-processing suitability, especially preventing deterioration of barrier properties that prevent the transmission of oxygen gas, water vapor, etc. of the film raw material, An object of the present invention is to provide a transparent barrier film wound material useful for filling and packaging various articles.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has used a vacuum evaporation apparatus or the like in which the inside is evacuated and used a paper roll or the like to start the process. The raw material film is continuously supplied, and then, a deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is laminated on one side of the base film in a deposition chamber, and then the film is taken up and rolled. When wound up, on one side of the substrate film,
In the longitudinal direction, at least every 2000 to 8000 m in the longitudinal direction, at least 10 m to the right or left in the width direction.
By winding the film at an interval of m or less, it is possible to prevent blocking of the film in the form of winding the film, and the film can be peeled off very easily during post-processing. Anti-breaking, preventing the deterioration of the physical properties of the film raw material, etc., has extremely excellent post-processing suitability, particularly, the oxygen gas that the film raw material has,
The present invention has been found to prevent the deterioration of the barrier property for preventing the permeation of water vapor and the like, and to produce a raw material for winding a transparent barrier film useful for filling and packaging various articles such as food and drink. Is completed.

[0005] That is, the present invention relates to a base film having an inorganic oxide vapor-deposited film provided on one surface of a base film,
In the longitudinal direction, at least 2000 to 800
The present invention relates to a raw material for winding a transparent barrier film, characterized in that winding is performed at a distance of 10 mm or less to the right or left at least every 0 m in the width direction.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to the drawings. First, an example of the raw material for winding a transparent barrier film according to the present invention will be described with reference to the drawings and the like. FIG. 1 shows that one side of a base film is made of an inorganic material by a chemical vapor deposition method. FIG. 2 is a schematic configuration diagram showing a schematic configuration of a plasma chemical vapor deposition apparatus for producing a film raw material provided with an oxide deposition film, and FIG. FIG. 3 is a schematic configuration diagram showing a schematic configuration of a roll-to-roll vacuum vapor deposition apparatus for producing a film raw material provided with an inorganic oxide vapor deposition film on the surface of FIG. 3, and FIG. FIG. 4 is a schematic perspective view showing a configuration of an example of a film winding material, and FIG.
FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a film raw material provided with a vapor-deposited film of an inorganic oxide on one surface of a base film constituting a raw material roll of a transparent barrier film according to the present invention. .

First, the transparent barrier film according to the present invention is wound on one side of a substrate film constituting a raw material roll,
The raw film provided with the inorganic oxide vapor-deposited film is usually a film that can be produced by a chemical vapor deposition method, a physical vapor deposition method, or a combination of both. In the present invention, the method of forming a deposited film of an inorganic oxide by the chemical vapor deposition method described above will be described in more detail. Chemical vapor deposition methods such as a vapor phase growth method, a thermochemical vapor deposition method, and a photochemical vapor deposition method.
n method, CVD method) and the like. In the present invention, specifically, on one surface of the base film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. Further, an oxygen oxide gas or the like is used as a reaction gas with a monomer gas for vapor deposition, and a vapor-deposited film of an inorganic oxide such as silicon oxide is formed by a low-temperature plasma chemical vapor deposition method using a low-temperature plasma generator or the like. Can be formed. In the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method for forming a vapor-deposited film of an inorganic oxide by the low-temperature plasma enhanced chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method of forming an oxide deposition film. As shown in FIG. 1 described above, in the present invention, a vacuum chamber of a plasma enhanced chemical vapor deposition apparatus 11 is used.
The base film 1 is unwound from an unwinding roll 13 disposed in the inside 12, and the base film 1 is further transferred to an auxiliary roll.
The cooling / electrode drum 15 is conveyed onto the peripheral surface of the cooling / electrode drum 15 at a predetermined speed via the nozzle 14. Thus, in the present invention, the monomer for vapor deposition of oxygen gas, inert gas, organic silicon compound or the like is supplied from the gas supply devices 16 and 17 and the raw material volatile supply device 18 and the like.
While supplying a gas, etc., and adjusting the mixed gas composition for vapor deposition comprising them, the mixed gas composition for vapor deposition is introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and the above cooling / cooling is performed. The glow discharge plasma 20 is placed on the substrate film 1 transported on the peripheral surface of the electrode drum 15.
In this way, a plasma is generated, and the mixed gas for deposition is reacted in a plasma atmosphere to form a deposited film of an inorganic oxide such as silicon oxide. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 15 from a power source 21 arranged outside the vacuum chamber 12, and the cooling / electrode drum 15 is , A magnet 22 is arranged to promote the generation of plasma. Next, the base film 1 on which the vapor-deposited film of the inorganic oxide such as silicon oxide is formed is wound up on a winding roll 24 via an auxiliary roll 23, and the plasma chemical vapor phase according to the present invention is obtained. An inorganic oxide deposited film can be formed by a growth method. In the figure, reference numeral 25 denotes a vacuum pump.

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

In the present invention, a specific example of a method of forming a thin film of an inorganic oxide by the above-described physical vapor deposition method is shown in FIG. 2. FIG. 2 is a schematic diagram showing an example of a roll-up type vacuum evaporation apparatus. FIG. As shown in FIG. 2, in a vacuum chamber 32 of a take-up type vacuum evaporation apparatus 31, a base film 1 unwound from an unwinding roll 33 is cooled through guide rolls 34 and 35 to a cooled core. -Guided to the singing drum 36; Thus, on the substrate film 1 guided on the cooled coating drum 36,
The evaporation source 38 heated in the crucible 37, for example, metal aluminum or aluminum oxide is evaporated,
Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 39 and, while supplying the same, a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed through the masks 40 and 40, Next, in the above, for example, the base film 1 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through guide rolls 35 ′ and 34 ′ and wound up on a take-up roll 41. In addition, a deposited film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention.

As shown in FIG. 3 and FIG. 4, the raw material A for winding the transparent barrier film according to the present invention is as follows.
As in the above-described chemical vapor deposition method or physical vapor deposition method, a low-temperature plasma-enhanced chemical vapor deposition apparatus or a vacuum vapor deposition apparatus is used, and a base material is fed from a roll such as an unwinding roll. The film 1 is continuously supplied, and then a deposition film 2 of an inorganic oxide such as silicon oxide or aluminum oxide is laminated on one side of the base film 1 in a deposition chamber (see FIG. 3). A film roll 1a provided with an inorganic oxide vapor-deposited film 2 on one surface of a roll 1 is taken up on a roll 24.
(41) A film raw material 1a in which an inorganic oxide vapor-deposited film 2 is provided on one surface of a substrate film 1 when wound up.
At least in the longitudinal direction P
At least every 8000 m, in the width direction q, at least within a range of 10 mm or less to the right or left, the distance between them is shifted, preferably about 5 mm. Is what you do. In the present invention, as a raw material for winding a transparent barrier film according to the present invention, although not shown, a film raw material provided with a vapor-deposited inorganic oxide film on one surface of a base film,
In the longitudinal direction, every 2000 m, in the width direction, within a range of 10 mm or less to the right or left, the interval is shifted, preferably, the interval is shifted by about 5 mm. The film roll is the most desirable. Thus, the above example:
The present invention exemplifies 12 examples of the rolled-up raw material of the transparent barrier film according to the present invention, and the present invention is not limited thereto. For example, in the present invention, although not shown, the above-mentioned inorganic oxide vapor-deposited film is not only a single layer film but also a multilayer film or a composite film composed of two or more layers of the same or different inorganic oxide vapor-deposited films. It may be a film or the like, and it can be manufactured by designing a laminated material having various forms by further laminating other base materials arbitrarily according to the purpose of use, application, and the like.

Next, in the present invention, the material constituting the raw material for winding the transparent barrier film, the laminated material, the packaging container, etc., the production method and the like according to the present invention will be described in more detail. As a base film that constitutes a transparent barrier film rolled up material, packaging container, etc., when it constitutes a packaging container, it becomes a basic material, so it is mechanical, physical, chemical, etc. In particular, a resin film or sheet having strength, toughness, and heat resistance can be used. Specifically, in the present invention,
As the base film, for example, polyethylene resin,
Polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile
Styrene copolymer (AS resin), acrylonitrile-
Butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate, etc. Polyester resins, polyamide resins such as nylon, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins And films or sheets of various resins such as polyurethane resins, acetal resins, cellulose resins, and others. In the present invention, it is particularly preferable to use a film or sheet of a polypropylene resin, a polyester resin, or a polyamide resin.

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

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,
Antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, coloring agents such as dyes and pigments, and the like can be used. Can also be used.

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

Next, in the present invention, the above-mentioned inorganic oxide such as silicon oxide and aluminum oxide which constitutes the raw material for winding the transparent barrier film according to the present invention, a laminated material, a packaging container, and the like may be used. In addition, not only one layer of the deposited film of the inorganic oxide but also a multilayer film in which two or more layers are laminated may be used, and the material used may be one kind or a mixture of two or more kinds. It is also possible to form a deposited film of an inorganic oxide mixed with the above materials. For example, in the present invention, a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above is used to first form an inorganic oxide deposited film as the first layer, and then deposit the inorganic oxide in the same manner. On the film, an inorganic oxide vapor-deposited film is further formed, or by using a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above, this is connected in series, and the inorganic oxide is continuously formed. By forming a vapor deposition film of above, a vapor deposition film of an inorganic oxide composed of a multilayer film of two or more layers can be formed. Note that, in the present invention, first, a first-layer inorganic oxide vapor-deposited film is formed by using the above-described roll-up vacuum vapor deposition apparatus,
Next, in the same manner, an inorganic oxide vapor deposition film is further formed on the inorganic oxide vapor deposition film, or this is rolled up in duplicate using the above-mentioned winding vacuum vapor deposition apparatus. By continuously forming a vapor-deposited film of an inorganic oxide, a vapor-deposited film of an inorganic oxide composed of a multilayer film of two or more layers can be formed.

In the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like 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. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, the silicon oxide vapor-deposited film formed above reacts chemically with a monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is formed on one side of the weather-resistant base material layer. closely wear surface, dense, it is possible to form a thin film rich in flexibility or the like, usually, the general formula SiO _X (where
X represents a number from 0 to 2), and is a continuous vapor-deposited film mainly composed of silicon oxide. Thus, the above silicon oxide vapor-deposited film is represented by the general formula SiO _X (where X represents a number from 1.3 to 1.9) in terms of transparency, barrier properties, and the like. It is preferably a thin film mainly composed of a deposited silicon oxide film. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has It has a yellow color and poor transparency. Further, the above-described deposited film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or both elements Consisting of a deposited film of silicon oxide containing as a trace constituent element, and having a thickness of 50 °
The angle is in the range of 4000 °, and the composition ratio of the essential constituent elements and the trace constituent elements continuously changes in the film thickness direction. Further, when the silicon oxide vapor-deposited film contains a compound composed of carbon, the content of carbon is reduced in the depth direction of the film thickness.

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

In the present invention, as the above-mentioned inorganic oxide vapor-deposited film formed by using the above-mentioned roll-up type vacuum evaporator or the like, basically any thin film on which a metal oxide is vapor-deposited 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 deposited film of an oxide of a metal such as zirconium (Zr) or yttrium (Y) can be used. Thus, a preferable example is a deposited film of an oxide of a metal such as silicon (Si) and aluminum (Al). Thus, the above-mentioned vapor-deposited film of a metal oxide can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. The notation is, for example, SiO _x , AlO _x , MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as such MgO _X represented by. The range of the value of X is 0 to 2 for silicon (Si) and 0 to 2 for aluminum (Al).
1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0, potassium (K) is 0-0.5,
Tin (Sn) is 0-2, and sodium (Na) is 0-2.
0.5, boron (B) is 0-1,5, titanium (Ti)
Is 0-2, lead (Pb) is 0-1, zirconium (Z
r) can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 1.5. In the above, when X = 0, it is a perfect metal, it is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention, generally, silicon (S
i), except for aluminum (Al), few examples are used. Silicon (Si) has a value in the range of 1.0 to 2.0, and aluminum (Al) has a value in the range of 0.5 to 1.5. Can be used. In the present invention, the thickness of the above-mentioned inorganic oxide vapor-deposited film varies depending on the type of metal or metal oxide to be used.
It is desirable to arbitrarily select and form the thickness in the range of about 2000 to about 2000, preferably about 100 to about 1000. Further, in the present invention, as the inorganic oxide deposited film,
As a metal or a metal oxide to be used, one kind or a mixture of two or more kinds may be used to form a vapor deposited film of an inorganic oxide mixed with different materials.

In the present invention, as the inorganic oxide vapor-deposited film constituting the raw material for winding the transparent barrier film of the present invention, a laminate, a packaging container, etc., for example,
It is also possible to form and use a composite film composed of two or more layers of vapor deposited films of different inorganic oxides by using both the physical vapor deposition method and the chemical vapor deposition method described above. Thus,
As a composite film composed of two or more layers of the above-mentioned different kinds of inorganic oxide vapor-deposited films, first, a dense, flexible, and relatively crack-free film is formed on a base film by a chemical vapor deposition method. A deposited film of an inorganic oxide capable of preventing generation is provided, and then a deposited film of an inorganic oxide formed by physical vapor deposition is provided on the deposited film of the inorganic oxide to form a composite film comprising two or more layers. It is desirable to form a deposited film of an inorganic oxide consisting of Of course, in the present invention, contrary to the above, an inorganic oxide vapor-deposited film is first provided on the base film by physical vapor deposition and then densely deposited by chemical vapor deposition. In addition, it is also possible to provide a deposited film of an inorganic oxide which is rich in flexibility and can relatively prevent the occurrence of cracks, thereby forming a deposited film of an inorganic oxide composed of a composite film composed of two or more layers. is there.

In the present invention, the raw material of the transparent barrier film according to the present invention is obtained by laminating, for example, at least a heat-sealing resin layer on the surface of the inorganic oxide vapor-deposited film. It is possible to produce a packaging material by using the laminated material, producing a packaging container in various forms by bag-making or box-making, and filling and packaging various articles to produce a packaged product. . In the above, the heat-sealing resin layer can be constituted by using, for example, various resins that can be melted by heat and fused to each other. Specifically, for example, low-density polyethylene, Medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-α-olefin copolymer polymerized using a 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, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, Acrylic acid, methacrylic acid, maleic Phosphate, maleic acid anhydride,
Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as fumaric acid and itaconic acid, polyvinyl acetate resins,
Poly (meth) acrylic resin, polyvinyl chloride resin,
The heat-sealing resin layer can be formed by using other resins.

Next, in the present invention, the above-mentioned base film can be similarly used as a material for producing a laminated material by laminating the transparent barrier film according to the present invention. Thus, in the present invention, as the base film, for example, when constituting a packaging container, since it is a basic material, it has excellent properties in mechanical, physical, chemical, etc., In particular, a resin film or sheet having strength, toughness, and heat resistance can be used, and specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, and a polyolefin. Resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin,
Other tough resin films or 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 about 10 μm to 50 μm. In the present invention, the base film as described above is subjected to, for example, front printing or back printing by printing a desired printing pattern such as a character, a figure, a symbol, a picture, or a pattern by a normal printing method. It may be.

Next, in the present invention, as the base film, for example, various paper base materials constituting a paper layer can be used.
The paper base material is provided with shapeability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard, A paper substrate such as a processed paper or the like can be used. In the above, the paper base constituting the paper layer has a basis weight of about 80 to
600 g / m ² , preferably about 100-200 g / m ²
It is desirable to use a material of about 450 g / m ² . Needless to say, in the present invention, a paper base constituting the paper layer and various resin films or sheets as the base films mentioned above can be used in combination.

Next, in the present invention, as a material constituting a laminate using the raw material of the transparent barrier film according to the present invention, for example, low-density polyethylene having a barrier property against water vapor, water, etc., medium density polyethylene , High-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer and other resin films or sheets, or polyvinylidene chloride and polyvinyl alcohol having a barrier property against oxygen, water vapor, etc. A film or sheet of a resin such as saponified ethylene-vinyl acetate copolymer, a colorant such as a pigment added to the resin, and other desired additives. Colored resin film or sheet
Can be used. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but is usually about 5 μm to 300 μm, and more preferably about 10 μm.
m to 100 μm is desirable.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the laminated 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, Rupentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylnitrile 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 the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. Further, in the present invention, as the film or sheet, extrusion film formation,
Any film such as an inflation film or a coating film may be used. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used.

Next, in the present invention, as a method for producing a laminated material using the transparent barrier film raw material according to the present invention, for example, the inorganic material of the above-mentioned transparent barrier film raw material according to the present invention is used. First, on the surface of the oxide deposited film,
If necessary, a primer agent layer is provided, and further, the above-mentioned anchor coat agent layer is formed on the surface of the primer agent layer,
Thereafter, the above-mentioned heat-sealing resin is used through the primer agent layer and the anchor coating agent layer and the like, for example, by using a T-die co-extrusion lamination method or the like. The laminated material according to the present invention can be manufactured by laminating the layers while coextruding them and laminating the heat-sealing resin layer. Alternatively, in the present invention, first, if necessary, a primer agent layer is provided on the surface of the above-mentioned inorganic oxide vapor-deposited film of the transparent barrier film according to the present invention, and further, the primer agent The above-mentioned anchor coating agent layer is formed on the surface of the layer, and thereafter, the above-mentioned heat-sealing agent is interposed via the primer agent layer and the anchor coating agent layer.
The laminated material according to the present invention can be manufactured by extruding a heat-sealing resin film or sheet and laminating the same using a thermosetting resin or the like. Next, in the present invention, first, if necessary, a primer agent layer is formed on the surface of the inorganic oxide vapor-deposited film of the raw material of the transparent barrier film according to the present invention, and then the primer is formed. −
A laminating adhesive layer is formed on the surface of the agent layer, and thereafter, the heat-sealing resin film or film is formed via the primer agent layer and the laminating adhesive layer. The laminate according to the present invention can be manufactured by laminating sheets or the like using a dry laminating lamination method. In the present invention, the thickness of the heat-sealing resin layer is about 10 μm to 200 μm, preferably about 20 μm to 100 μm.

In the present invention, as the primer agent layer constituting the laminated material, for example, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, (meth) Using a resin composition containing an acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of a vehicle. Primer
An agent layer can be formed. In the present invention, a primer coating agent layer is formed by coating using a coating method such as roll coating, gravure coating, kiss coating, or the like. It is possible,
Thus, the coating amount is 0.1 to 10 g.
/ M ² (dry state).

In the present invention, the anchor coating agent layer constituting the above-mentioned laminated material will be described. The anchor coating agent constituting such an anchor coating agent layer is, for example, an alkyl titanate. Water-based or oil-based various anchors such as organic titanium-based, isocyanate-based, polyethyleneimine-based, polybutadiene-based, etc.
Agent can be used. The above-mentioned anchor coating agent can be coated by using a coating method such as roll coating, gravure roll coating, kiss coating and others. As quantity,
It is desirably about 0.1 to 5 g / m ² (dry state).

Furthermore, in the present invention, the laminating adhesive layer constituting the above-mentioned laminated material will be described.
Examples of the adhesive constituting the adhesive layer for laminating include, for example, a polyvinyl acetate adhesive, a homopolymer such as ethyl, butyl, and 2-ethylhexyl acrylate, or a combination thereof with methyl methacrylate or acrylonitrile. Adhesives, cyanoacrylate adhesives, copolymers of ethylene with monomers such as vinyl acetate, ethyl acrylate, ethyl acrylate, methacrylic acid, etc. An ethylene copolymer adhesive, a cellulose adhesive,
Polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, reactive type ( (Meth) acrylic adhesives, rubber adhesives composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, inorganic adhesives composed of alkali metal silicate, low melting point glass, etc. And the like. The composition system of the above-mentioned adhesive may be any composition form 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, and a solid. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a heat pressure type. The above adhesive can be applied by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. The coating amount is desirably about 0.1 to 10 g / m ² (dry state).

In the present invention, in the laminate using the transparent barrier film raw material according to the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminate. is there. Thus, the printed pattern layer contains one or more of ordinary ink vehicles as main components, and if necessary, a plasticizer,
Optionally adding one or more additives such as stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, etc., Colorants such as dyes and pigments are added, and the ink composition is adjusted by sufficiently kneading with a solvent, a diluent, etc., and then using the ink composition, for example, gravure printing, offset printing, letterpress printing, Using a printing method such as screen printing, transfer printing, flexographic printing, etc., a desired printing pattern consisting of characters, figures, symbols, patterns, etc. is printed on the above-mentioned coating thin film, and the book is printed. The printed pattern layer according to the invention can be formed.

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 the laminated material manufactured in such a manner, the heat-sealing film of the inner layer is opposed to the surface, and the heat-sealing film is folded, or the two sheets are overlapped, and the peripheral edge is further heated. -A bag can be formed by sealing and providing a seal portion. Thus, as a bag-making method, the above-mentioned laminated material is bent with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further sealed with, for example, a side sheet. Seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seal type),
Heat seals such as pleated seal type, flat bottom seal type, square bottom seal type, etc., to form packaging containers of various forms according to the present invention. Can be manufactured. In addition, for example, a self-standing packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the above-described laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotating roll seal,
It can be carried out by a known method such as a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal, and the like. 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, the packaging container manufactured as described above can be used for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other articles. It is used for filling and packaging. Thus, in the present invention, particularly, for example, soy sauce, source,
Small bags for liquids for filling and packaging soups, bags for soft packaging for filling and packaging raw confectionery, or curries, stews, soups
It is useful as a packaging container for filling and packaging liquid foods or drinks containing water or the like, such as soft packaging bags for filling and packaging boil or retort foods and the like such as bottles, hamburgers and the like.

[0035]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 (1). A 15 μm-thick biaxially stretched nylon 6 film (width, 1000 mm, length, 15000 m, single-sided corona treatment) was used, and this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. Under the vapor deposition conditions, a vapor-deposited silicon oxide film having a thickness of 200 ° was formed on the corona-treated surface of the biaxially stretched nylon 6 film. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm) Vacuum chamber-internal vacuum degree: 2-6 0.0 × 10 ⁻⁶ mbar Degree of vacuum inside the deposition chamber; 2 to 6.0 × 10 ⁻³ mbar Line speed; 100 m / min Cooling / electrode drum supply power; 10 kW Immediately after forming the deposited film, the surface of the deposited silicon oxide film was subjected to power of 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2 by using a glow discharge plasma generator. 5 (unit: slm) using a mixed gas pressure of 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
Plasma treatment with an argon mixed gas was performed to form a plasma treated surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more. In addition, vapor deposition under the above conditions, and further, while performing plasma treatment, a biaxially stretched nylon 6 film every 2000 m of vapor deposition distance,
By operating an edge position controller (EPC), the biaxially stretched nylon 6 film on which a 200-mm-thick silicon oxide vapor-deposited film is formed is shifted left and right with a gap of 5 mm in a vacuum chamber. The transparent barrier film according to the present invention was produced by winding the film on a winding roll. Next, when the transparent barrier film raw material produced above was taken out of the vacuum chamber and the transparent barrier film raw material was rewound, adhesion of the end portion thereof,
No releasability failure was observed. Furthermore, no breakage of the film due to poor releasability at the time of post-processing such as slit processing, deformation of the film, etc. are not recognized.
Cracks and the like can be prevented from being generated in the deposited film of silicon oxide, the deterioration of the barrier property can be suppressed, and the production efficiency can be improved. (2). Next, using a gravure printing ink composition, a desired printing pattern is formed by a gravure printing method on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film raw material produced above, and then the printing is performed. An anchor coating agent consisting of a 7% ethyl acetate solution of a two-pack curable polyurethane resin consisting of polyetherpolyol and isocyanate is used on the entire surface including the pattern, and this is a gravure roll coat. 0.5 g / m ² (dry state)
To form an anchor coating agent layer. Further, on the surface of the anchor coating agent layer formed above, a linear low density polyethylene resin layer having a thickness of 60 μm was formed by using a linear low density polyethylene and extruding them. Was manufactured. (3). Next, two sheets of the laminated material manufactured as described above are prepared, and the surfaces of the linear low-density polyethylene resin layers are superposed on each other.
A three-way seal-type soft packaging pouch having a seal portion formed by sealing and having an opening at an upper portion was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured. The liquid sachet packaging product produced above is excellent in barrier properties against oxygen gas, water vapor, etc., and excellent in fragrance retention, no alteration of its contents is observed, and
It was excellent in strength and the like, withstanding distribution in the market, and excellent in storage and preservation.

Embodiment 2 (1). In Example 1 described above, while performing vapor deposition, and then performing plasma treatment, the biaxially stretched nylon 6 film was operated for every 8000 m of vapor deposition distance by an edge position controller (EPC) so that a gap having a deviation width of 5 mm was formed. In the same manner as in Example 1 except that the biaxially stretched nylon 6 film on which a silicon oxide deposited film having a thickness of 200 ° was formed was shifted to the left and right and wound around a winding roll in a vacuum chamber. Thus, a raw material of a transparent barrier film according to the present invention was produced. Next, the raw material of the transparent barrier film produced above was taken out of the vacuum chamber, and the raw material of the transparent barrier film was rewound. However, no problem was observed. Furthermore, no breakage of the film due to poor releasability during post-processing such as slitting, deformation of the film, and the like are not observed, and at this time, it is possible to prevent the occurrence of cracks and the like in the deposited silicon oxide film. As a result, the deterioration of the barrier property was suppressed, and the production efficiency was improved. (2). Next, using a gravure printing ink composition, a desired printing pattern is formed by a gravure printing method on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film raw material produced above, and then the printing is performed. A two-component curable polyurethane-based laminating adhesive was used on the entire surface including the pattern, and this was applied to a film thickness of 4.0 g / m ² (dry state) by a gravure roll coating method in the same manner as described above. ) To form a laminating adhesive layer.
Next, a 60 μm-thick linear low-density polyethylene film was opposed to the laminating adhesive layer surface formed above, and both were dry-laminated to produce a laminated material according to the present invention. . (3). Next, two sheets of the laminated material manufactured as described above are prepared, and the surfaces of the linear low-density polyethylene film are superimposed on each other, and thereafter, the end around the outer periphery is heat sealed three-way to seal. A three-way seal-type soft packaging pouch having a sealing portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft packaging pouch produced above, and then the opening is sealed.
The upper seal portion was formed by sealing to produce a liquid pouch packaged product. The liquid sachet packaging product produced above is excellent in barrier properties against oxygen gas, water vapor, etc., excellent in fragrance retention, does not show any deterioration in its contents, and has excellent laminate strength, etc. And excellent in storage and preservation.

Embodiment 3 (1). Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (width, 1000 mm, length, 15,000
m), a 200-mm-thick silicon oxide vapor-deposited film was formed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film in exactly the same manner as in Example 1 above. A plasma treated surface was formed on the surface of the deposited silicon oxide film of 200 °. Oh, while depositing under the above conditions, and further performing plasma treatment, the edge position controller (EPC) was operated for every 2000 m of the biaxially stretched polyethylene terephthalate film, and the displacement width was 5 mm. The biaxially stretched polyethylene terephthalate film on which a 200-nm-thick silicon oxide vapor-deposited film is formed is shifted to the left and right at an interval of 2 mm and wound up on a winding roll in a vacuum chamber according to the present invention. A transparent barrier film was produced. Next, the raw material of the transparent barrier film produced above was taken out of the vacuum chamber, and the raw material of the transparent barrier film was rewound. Was. Furthermore, no breakage of the film due to poor releasability during post-processing such as slitting, deformation of the film, and the like are not observed, and at this time, it is possible to prevent the occurrence of cracks and the like in the deposited silicon oxide film. As a result, the deterioration of the barrier property was suppressed, and the production efficiency was improved. (2). Next, a desired printed pattern is formed on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film raw material produced above in exactly the same manner as in Example 1 above. An anchor coat agent layer was formed on the entire surface including the coating. Next, a linear low-density polyethylene resin layer having a film thickness of 40 μm was extruded while using a linear low-density polyethylene on the surface of the anchor coating agent layer formed above while melting and extruding them. Thus, a laminated material according to the present invention was manufactured. (3). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the linear low-density polyethylene resin layers are superposed on each other.
A three-way seal-type soft packaging pouch having a seal portion formed by sealing and having an opening at the top was manufactured. The three-way seal-type soft packaging sachet is filled with soy sauce through its opening, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured. The liquid sachet packaging product produced above has excellent barrier properties against oxygen gas, water vapor, and the like, and also has excellent fragrance retention properties, and its contents are not altered.
It was excellent in strength and the like, withstanding distribution in the market, and excellent in storage and preservation.

Embodiment 4 (1). In Example 3 described above, the biaxially stretched polyethylene terephthalate film was deposited at every deposition distance of 8000 m by operating an edge position controller (EPC) while performing the vapor deposition and further performing the plasma treatment, to thereby obtain a deviation width of 5 mm.
The biaxially stretched polyethylene terephthalate film on which a 200-mm-thick silicon oxide vapor-deposited film was formed by shifting the film left and right at an interval of mm, was wound in a vacuum chamber in a winding roll. Exactly as in Example 3,
A transparent barrier film raw material according to the present invention was produced.
Next, the raw material of the transparent barrier film produced above was taken out of the vacuum chamber, and the raw material of the transparent barrier film was rewound. However, no problem was observed. Furthermore, no breakage of the film due to poor releasability during post-processing such as slitting, deformation of the film, and the like are not observed, and at this time, it is possible to prevent the occurrence of cracks and the like in the deposited silicon oxide film. As a result, the deterioration of the barrier property was suppressed, and the production efficiency was improved. (2). Next, the above Example 2 was applied to the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film formed above.
In the same manner as above, a desired print pattern is formed, and then a two-part curable polyurethane-based laminating adhesive is used on the entire surface including the print pattern formed above, and Similarly, a film thickness of 4.0 was obtained by a gravure roll coating method.
g / m ² (dry state) to form an adhesive layer for lamination. Next, a linear low-density polyethylene film having a thickness of 60 μm was dry-laminated on the surface of the laminating adhesive layer formed as described above to produce a laminated material according to the present invention. (3). Next, two sheets of the laminated material manufactured as described above are prepared, and the surfaces of the linear low-density polyethylene film are superimposed on each other, and thereafter, the end around the outer periphery is heat sealed three-way to seal. A three-way seal-type soft packaging pouch having a sealing portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft packaging pouch produced above, and then the opening is sealed.
The upper seal portion was formed by sealing to produce a liquid pouch packaged product. The liquid sachet packaging product produced above is excellent in barrier properties against oxygen gas, water vapor, etc., excellent in fragrance retention, does not show any deterioration in its contents, and has excellent laminate strength, etc. And excellent in storage and preservation.

Comparative Example 1 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, the corona-treated surface of the biaxially stretched nylon 6 film was formed in the same manner as in Example 1 to a thickness of 200 μm.
A silicon oxide vapor-deposited film was formed, and a plasma treated surface was further formed. In addition, the biaxially stretched nylon 6 film was deposited at a deposition distance of 200
At every 0 m, the edge position controller (EPC) is operated and shifted to the left and right at an interval of a shift width of 5 mm, and the biaxially stretched nylon 6 film on which a 200-mm-thick silicon oxide deposited film is formed is vacuum-evacuated. The film was not taken up on a take-up roll in the chamber, but was taken up on a take-up roll in a usual manner to produce a raw material of a transparent barrier film. In addition, the end of the transparent barrier film raw material,
It was rising upward. (2). Next, a desired printed pattern is formed on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film raw material produced above in exactly the same manner as in Example 1 above. An anchor coat agent layer was formed on the entire surface including the coating. Next, a linear low-density polyethylene was used on the surface of the anchor coating agent layer formed above, and these were melted and extruded to extrude a linear low-density polyethylene resin layer having a thickness of 60 μm. Thus, a laminated material was manufactured. (3). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the linear low-density polyethylene resin layers are superposed on each other.
A three-way seal-type soft packaging pouch having a seal portion formed by sealing and having an opening at the top was manufactured. The three-way seal-type soft packaging sachet is filled with soy sauce through its opening, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

Comparative Example 2 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was coated on the corona-treated surface in exactly the same manner as in Example 3 above. 20
A 0 ° silicon oxide deposited film was formed, and a plasma treated surface was further formed. The biaxially stretched polyethylene terephthalate film was vapor-deposited and further subjected to plasma treatment, and the edge position controller (EPC) was operated at a vapor deposition distance of 2000 m every left and right with a gap of 5 mm in width. The biaxially stretched polyethylene terephthalate film on which a 200-mm-thick silicon oxide vapor-deposited film is formed is not wound up on a winding roll in a vacuum chamber, but is wound up in a usual manner. The resultant was wound into a roll to produce a transparent barrier film. In addition, the edge of the above-mentioned transparent barrier film raw material was raised upward. (2). Next, a desired printed pattern is formed on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film raw material produced above in exactly the same manner as in Example 3 above. An anchor coat agent layer was formed on the entire surface including the coating. Next, a linear low-density polyethylene was used on the surface of the anchor coating agent layer formed above, and these were melted and extruded to extrude a linear low-density polyethylene resin layer having a thickness of 60 μm. Thus, a laminated material was manufactured. (3). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the linear low-density polyethylene resin layers are superposed on each other.
A three-way seal-type soft packaging pouch having a seal portion formed by sealing and having an opening at the top was manufactured. The three-way seal-type soft packaging sachet is filled with soy sauce through its opening, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

EXPERIMENTAL EXAMPLES Regarding the raw materials of the transparent barrier films produced in Examples 1 to 4 and Comparative Examples 1 and 2, the oxygen permeability, the water vapor permeability, the blocking state, and the maximum line speed capable of slitting were determined. It was measured. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is a condition of temperature of 40 ° C and humidity of 90% RH in the United States,
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. (3). Measurement of blocking state This was confirmed by observing the raw transparent barrier film while peeling it off. (4). Measurement of maximum line speed at which slitting is possible This was measured at a line speed at which the raw material of the transparent barrier film was slit while being peeled off and wound on a small winding roll. The above measurement results are shown in Table 1 below.

[0042] 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 maximum line speed that can be slit is [m / min].

As is evident from the measurement results shown in Table 1 above, the samples of Examples 1 to 4 were all superior to those of Comparative Examples 1 and 2.

[0044]

As is apparent from the above description, the present invention uses a vacuum evaporation apparatus or the like in which the inside is evacuated, continuously supplies the base film from a paper feed roll or the like, After laminating a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide on one side of the substrate film in a vapor deposition chamber, one side of the substrate film is taken up when the film is taken up on a take-up roll or the like. A film raw material provided with an inorganic oxide vapor-deposited film on the surface of
Every 0 to 8000 m, in the width direction, at least, with a 5 mm shift to the right or to the left, to prevent winding of the raw film in the form of winding the raw film, and to prevent the occurrence of blocking of the raw film during post-processing. It can exfoliate the film raw material very easily, prevents breakage of the film raw material, deterioration of the physical properties of the film raw material, etc., and has extremely excellent post-processing suitability. It is possible to prevent the deterioration of the barrier property for preventing the permeation of gas, water vapor and the like, and to produce a transparent barrier film wound material useful for filling and packaging various articles such as food and drink. Things.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of a plasma chemical vapor deposition apparatus.

FIG. 2 is a schematic configuration diagram illustrating an example of a take-up type vacuum evaporation apparatus.

FIG. 3 is a schematic diagram showing an example of a layer structure of a film raw material in which an inorganic oxide vapor-deposited film is provided on one surface of a base film constituting a raw material of a transparent barrier film according to the present invention. It is sectional drawing.

FIG. 4 is a schematic perspective view showing an outline of an example of the configuration of an original transparent barrier film according to the present invention.

[Explanation of symbols]

 A Raw material of transparent barrier film 1a Raw film 1a Base film 2 Deposited film of inorganic oxide p Length direction q Width direction

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C23C 16/54 C23C 16/54 F term (reference) 3E067 AA03 AA11 AB01 AB16 AB26 AB28 AB81 AB96 BA12A BB01A BB12A BB14A BB15A BB16A BB18A BB22A BC03A BC06A CA05 CA06 CA11 CA12 CA17 EA07 EA08 EA09 EE02 EE32 FB07 GD01 GD02 3F055 AA05 BA01 BA06 CA01 DA01 FA05 FA17 4K029 AA11 BA03 BA44 BB01 CA02

Claims (4)

[Claims] 1. A film raw material having an inorganic oxide vapor-deposited film provided on one surface of a substrate film, at least every 2000 to 8000 m in the longitudinal direction and at least right or left in the width direction. A transparent barrier film roll, wherein the roll is wound at a distance of 10 mm or less. 2. A film raw material having an inorganic oxide vapor-deposited film provided on one surface of a base film is placed on the right or left side in the width direction at every 2000 m in the longitudinal direction.
A raw material for winding a transparent barrier film, wherein the raw material is wound at an interval of 0 mm or less. 3. The raw material for winding a transparent barrier film according to claim 1, wherein the base film comprises a biaxially stretched resin film or sheet. 4. The transparent barrier according to claim 1, wherein the deposited inorganic oxide film comprises a deposited inorganic oxide film formed by a chemical vapor deposition method or a physical vapor deposition method. Film roll.