JPH11348171A - Transparent barrier film and laminated body using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have gas barrier properties against oxygen gas, steam or the like even under the condition that cracks, pinholes or the like develop in deposited films and become suitable for the filling packaging of various articles by a method wherein two or more layers of the deposited film of an inorganic oxide are superposed by a plasma chemical deposition method on one side of a base material film. SOLUTION: On one side of a base material film 2, a second inorganic oxide deposited film 3b is provided by a plasma chemical deposition method on a first inorganic oxide deposited film 3a similarly been provided by the plasma chemical deposition method. In the plasma chemical deposition method, when a depositing mixed gas composition consisting of a depositing monomer gas made of an organic silicon compound or the like, an oxygen gas, an inert gas and the like is introduced in a vacuum chamber, the content of the oxygen gas in the composition is raised and that of the monomer gas is lowered, resulting in improving respective adhesions between the base material film and the deposited film and between the deposited films, the oxygen gas barrier properties of the film and its transparency. As a result, a film, which is excellent in transparency and has excellent gas barrier properties against the oxygen gas, the steam and the like and is suitable for the filling packaging of eatables and drinkables and various articles, is realized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent barrier film and a laminate using the same, and more particularly, to a film having excellent transparency, a barrier property against oxygen gas or water vapor, etc. The present invention relates to a transparent barrier film useful as a packaging material for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, electronic components, and the like, and a laminate using the same.

[0002]

2. Description of the Related Art Conventionally, various packaging materials having excellent oxygen gas barrier properties and water vapor barrier properties have been developed and proposed. One of them has recently been a substrate such as a plastic film. On one side of the film, using physical vapor deposition, or chemical vapor deposition, etc.,
For example, a deposition film provided with a deposition film of an inorganic oxide such as silicon oxide and aluminum oxide has been proposed. This is excellent in oxygen gas barrier properties, water vapor barrier properties, etc.,
In addition, it has attracted attention as a packaging material that has transparency and is environmentally friendly. In recent years, it has been laminated with other plastic films or packaging materials such as paper base materials, for example, food and drink, pharmaceuticals, and cosmetics. It is possible to manufacture a packaging container suitable for filling and packing various articles such as detergents, detergents, and the like, and the demand for such containers is expected to increase.

[0003]

However, the above-mentioned vapor-deposited film certainly has excellent transparency and
Although the oxygen gas barrier property and the water vapor barrier property are improved, the laminated film as a packaging material is manufactured by using the vapor-deposited film and laminating a film of another resin thereon.
Further, using the laminated body, to manufacture packaging containers of various forms from this, in the packaging container,
Even if various articles are filled and packed, not all packaging containers can produce a fully satisfactory packaged product. For example, in the above vapor deposition film,
On one surface of the substrate film, using a plasma-enhanced chemical vapor deposition method, in a deposited film provided with a deposited film of an inorganic oxide such as silicon oxide, the deposited film of the inorganic oxide such as silicon oxide is glass Since it is formed of a quality vapor-deposited film, there is a problem that cracks and the like are easily generated after vapor deposition, for example, in post-processing such as printing, laminating, or bag making. Thus, cracks and the like generated on the surface of the deposited film of the inorganic oxide such as silicon oxide as described above propagate not only on the surface of the deposited film but also in the depth direction of the deposited film, and as a result, The barrier properties of oxygen gas, water vapor, etc. are remarkably reduced and are no longer necessary as a barrier material. For example, a laminate of another resin film is manufactured by laminating a film of another resin. And then
Even if a packaging container is manufactured using the laminate and a variety of articles are filled and packaged in the packaging container to manufacture a packaged product, the commercial value of the product is significantly impaired. There is a problem that it cannot be used for such purposes. In addition, in one of the surfaces of the base film, a vapor-deposited film provided with a vapor-deposited film of an inorganic oxide such as silicon oxide using a plasma-enhanced chemical vapor deposition method includes a vapor deposition monomer gas, an oxygen gas, and an inert gas. , A non-reacted monomer for vapor deposition during the film formation, since a vapor-deposited film of an inorganic oxide such as silicon oxide is formed using a mixed gas composition for vapor deposition comprising There is a problem that a gas or the like is often included in the deposited film. Thus, if the unreacted monomer gas for vapor deposition or the like is contained in the vapor-deposited film of an inorganic oxide such as silicon oxide as described above, this causes the generation of pinholes in the vapor-deposited film, As described above, when pinholes are generated in the deposited film, the barrier properties against oxygen gas, water vapor and the like are remarkably reduced, and as described above, the barrier material does not need to be used. However, there is a problem that even if a packaged product is manufactured by filling and packaging the product, the commercial value of the product is significantly impaired, and a packaged product that is sufficiently satisfactory cannot be manufactured. Therefore, the present invention consists of a vapor-deposited film provided with a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide on one surface of a substrate film by plasma-enhanced chemical vapor deposition,
Furthermore, even if cracks, pinholes, etc. occur in the deposited film, they have excellent gas barrier properties against oxygen gas, water vapor, etc.
An object of the present invention is to provide a transparent barrier film useful for producing a packaging container or the like suitable for filling and packaging various articles, and a laminate using the same.

[0004]

As a result of various studies to solve the above problems, the present inventor has found that one surface of a substrate film is coated with an inorganic oxide such as silicon oxide by plasma-enhanced chemical vapor deposition. In providing the deposited film of the substance, paying attention to providing the deposited film of the inorganic oxide in two or more layers, first, on one surface of the base film, a first chemical vapor deposition method was used. Making inorganic oxide deposited film,
Next, on the first inorganic oxide vapor-deposited film, a second inorganic oxide vapor-deposited film is formed by plasma-enhanced chemical vapor deposition in exactly the same manner as described above. A transparent barrier film is manufactured by laminating three or more layers of a vapor-deposited film of an inorganic oxide by a chemical vapor deposition method, and thus the inorganic oxide film finally formed into the transparent barrier film is formed. A laminated body is manufactured by laminating at least a heat-sealing resin film on the surface of the vapor-deposited film, and the laminated body is used to form a bag to produce a packaging container. When packaging products are manufactured by filling and packaging the contents inside, they have excellent transparency and high gas barrier properties against oxygen gas, water vapor, etc., for example, food and drink, pharmaceuticals, cosmetics, detergents, etc. Packaging suitable for filling and packaging various goods And it completed the present invention have found that it is possible to produce a laminate using a useful transparent barrier film and it producing use container or the like.

That is, the present invention provides a transparent barrier film characterized by comprising two or more layers of an inorganic oxide deposited film formed by plasma enhanced chemical vapor deposition on one surface of a substrate film. The present invention relates to a laminate using the same.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to the drawings. First, one example of the transparent barrier film according to the present invention and a laminate using the same is illustrated by way of example, and the layer constitution is shown. FIGS. 1 and 2 show one example of the transparent barrier film according to the present invention. FIG. 3 is a schematic cross-sectional view showing two example layer configurations, and FIG.
FIG. 4 is a schematic cross-sectional view showing an outline of the operation and effect of the transparent barrier film according to the present invention, and FIG. 4 shows a layer configuration of an example of a laminate using the transparent barrier film according to the present invention. It is a schematic sectional drawing.

First, as a transparent barrier film 1 according to the present invention, as shown in FIG. 1, a first inorganic oxide is deposited on one surface of a base film 2 by a plasma chemical vapor deposition method. A film 3a is provided, and then a second inorganic oxide deposited film 3b is provided on the first inorganic oxide deposited film 3a by the plasma chemical vapor deposition method as described above. The basic structure is such that the two layers 3a and 3b of the first inorganic oxide vapor deposition film 3a and the second inorganic oxide vapor deposition film 3b are provided in an overlapping manner. Further, the transparent barrier film 1a according to the present invention has the structure shown in FIG.
As shown in FIG. 1, on one surface of the base material film 2, as shown in FIG. 1 described above, a first inorganic oxide deposited film 3 a and a second inorganic oxide After providing the deposited film 3b, the deposited film 3b of the second inorganic oxide
Is further provided with a third inorganic oxide deposited film 3c by plasma enhanced chemical vapor deposition, and thus the first inorganic oxide deposited film 3a and the second inorganic oxide deposited film are deposited. Three layers 3a, 3b, 3 of the film 3b and the deposited film 3c of the third inorganic oxide
and c. In the present invention, although not shown, as the transparent barrier film according to the present invention, on one surface of the base film, an inorganic oxide vapor-deposited film formed by plasma-enhanced chemical vapor deposition is laminated to four or more layers. It is also possible to manufacture a device having the configuration provided in the above manner.

By the way, the transparent barrier film according to the present invention having the above-described structure is exemplified by the first example using the transparent barrier film 1 shown in FIG. 1 as shown in FIG. Inorganic oxide deposited film 3a and the second
By overlaying the two layers with the inorganic oxide deposited film 3b, the crack 4 is temporarily formed on the first inorganic oxide deposited film 3a.
a, 4a... occur, the cracks 4a, 4a.
If no cracks 4b, 4b,... Occur in the second inorganic oxide vapor-deposited film 3b located at the position corresponding to the position where the cracks occur, the crack 4a generated in the first inorganic oxide vapor-deposited film 3a described above. , 4a... Represent the second inorganic oxide deposited film 3
b, and the two layers of the first inorganic oxide vapor deposition film 3a and the second inorganic oxide vapor deposition film 3b have a synergistic effect. It is possible to maintain the barrier property against Therefore, in the transparent barrier film according to the present invention,
It is characterized in that two or more layers of an inorganic oxide deposited film by plasma enhanced chemical vapor deposition are stacked, but it is preferable to stack two or three layers in consideration of the production cost and the like. Things.

Next, as a laminate 11 using the transparent barrier film according to the present invention, as shown in FIG.
For example, as an example using the transparent barrier film 1 shown in FIG. 1 described above, first, as described above, the first surface of the base film 2 is formed on the first surface by the plasma chemical vapor deposition method.
And a second inorganic oxide deposited film 3a and a second inorganic oxide deposited film 3b.
Further, at least a heat-sealing resin layer 5 is provided on the surface of the inorganic oxide vapor-deposited film 3b constituting the transparent barrier film 1. The above-mentioned examples illustrate one or two examples of the transparent barrier film according to the present invention and the laminate using the same, and it goes without saying that the present invention is not limited thereby. .

Next, the above-mentioned transparent barrier film according to the present invention and a material constituting a laminate using the same,
The production method and the like will be described. First, as the transparent barrier film according to the present invention or the base film constituting the laminate, films or sheets of various colorless and transparent resins can be used. Specifically, for example, polyolefin resins such as polyethylene or polypropylene, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyamide resins, polycarbonate resins, polystyrene resins, Films or sheets of various resins such as polyvinyl alcohol-based resin, saponified ethylene-vinyl acetate copolymer, polyacrylonitrile-based resin, acetal-based resin and others can be used. As the resin film or sheet, for example, a tenter method or a tube method is used, and a film or sheet which is biaxially stretched in two directions such as length and width is also used. can do. As the resin film or sheet, a resin film or sheet obtained by forming a single layer or two or more layers by coextrusion and then biaxially stretching is also used. can do. Also,
In the present invention, the thickness of the base film can be appropriately set in consideration of the stability at the time of production of the film or sheet, but is about 5 to 100 μm, preferably 10 to 50 μm. Position is desirable. In the present invention, the base film is coated on the surface thereof in advance with a known primer coating agent, if necessary, in order to enhance the adhesion to the deposited film or the like. An agent layer or the like may be provided. The surface of the above-mentioned base film can be optionally subjected to a surface activation treatment such as a corona treatment, a plasma treatment, a framing treatment, etc., if necessary. In the present invention, depending on the application, for example, desired additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, and the like are arbitrarily added within a range not affecting the transparency. However, resin films or sheets containing them can also be used.

Next, in the present invention, the transparent barrier film of the present invention or the inorganic oxide vapor-deposited film formed by the plasma-enhanced chemical vapor deposition method constituting the laminate will be described. Surface, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, and a mixed gas composition for vapor deposition comprising the monomer gas for vapor deposition, oxygen gas, inert gas, and the like is used.
A plasma-enhanced chemical vapor deposition (CVD) method using a low-temperature plasma generator or the like having two or more silicon oxides or the like, and forming two or more inorganic oxide deposited films such as silicon oxide. The transparent barrier film according to the present invention can be formed. In the above description, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

More specifically, the above-described plasma chemical vapor deposition method will be described by way of example. FIG. 5 is a schematic configuration of a plasma chemical vapor deposition apparatus showing an outline of the plasma chemical vapor deposition method having two vacuum chambers. FIG. As shown in FIG. 5 described above, in the present invention, first, the base film 2 is fed out from the unwinding roll 33 arranged in the first vacuum chamber 32 of the plasma chemical vapor deposition apparatus 31, and further, The substrate film 2 is conveyed onto the peripheral surface of the cooling / electrode drum 35 at a predetermined speed via the auxiliary roll 34. Thus, in the present invention, the gas supply devices 36, 3
7, and an oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the raw material volatilizing supply device 38 and the like, and the raw material is adjusted while adjusting a mixed gas composition for vapor deposition composed of them. It is introduced into the vacuum chamber 32 through the supply nozzle 39, and is then glowed on the substrate film 2 conveyed on the cooling / electrode drum 35 peripheral surface.
Plasma 40 is generated by the discharge plasma, and the plasma 40 is irradiated to form a first deposited film of an inorganic oxide such as silicon oxide. In this case, in the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 35 from the power supply 41 arranged outside the vacuum chamber 32, and the cooling / electrode drum 35 is Is the magnet 42
And the generation of plasma is promoted,
The base film 2 on which the first inorganic oxide vapor-deposited film such as silicon oxide is formed is supplied through the auxiliary rolls 43 and 44 into the second vacuum chamber 45 constituting the plasma chemical vapor deposition apparatus 31. To supply. Thus, the base film 2 on which the first inorganic oxide or other inorganic oxide vapor-deposited film is supplied into the second vacuum chamber 45 constituting the plasma chemical vapor deposition apparatus 31 is used as the auxiliary film. -Via rules 46, 47,
Similarly to the above, the cooling / electrode drum 48 is conveyed on the peripheral surface at a predetermined speed. Thus, in the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition of an organic silicon compound, and the like are supplied from the gas supply devices 49 and 50 and the raw material volatilization supply device 51 and the like. The above-mentioned base material which was introduced into the second vacuum chamber 45 through the raw material supply nozzle 52 while adjusting the mixed gas composition for vapor deposition consisting of and was conveyed on the peripheral surface of the cooling / electrode drum 48 A plasma 53 is generated by glow discharge plasma on a vapor-deposited film of an inorganic oxide such as a first silicon oxide formed on the film 2 and is irradiated with the plasma 53 to form an inorganic film such as a second silicon oxide. The deposited film of the oxide is formed into a deposited film in which two layers of a deposited film of an inorganic oxide such as a first silicon oxide and a deposited film of an inorganic oxide such as a second silicon oxide are stacked. In addition,
In the present invention, the cooling / electrode drum 48
A predetermined power is applied from a power supply 54 disposed outside the vacuum chamber 45, and a magnet 55 is disposed near the cooling / electrode drum 48 to promote generation of plasma. Then, the above-mentioned base film 2 is formed by depositing a two-layer deposited film of an inorganic oxide deposited film such as a first silicon oxide and a second inorganic oxide deposited film such as a silicon oxide. Take-up roll 5 via roll 56
7, and a transparent base film 2 formed by laminating two layers of a deposited film of an inorganic oxide such as a first silicon oxide and a deposited film of an inorganic oxide such as a second silicon oxide. It can produce a barrier film. In the drawings, 58 and 59 represent vacuum pumps provided to evacuate the two vacuum chambers -32 and 45. The above example is an example of a plasma enhanced chemical vapor deposition method having two vacuum chambers according to the present invention. In the present invention, a plasma enhanced chemical vapor deposition method having three or more vacuum chambers is used. Using a chemical vapor deposition apparatus, three or more layers can be laminated to produce a transparent paria film, and it goes without saying that the present invention is not limited by the above examples.

In the above, a monomer for vapor deposition of an organic silicon compound or the like for forming a vapor deposited film of an inorganic oxide such as silicon oxide.
As the gas, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, 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 above-mentioned organosilicon compounds, 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 characteristics and the like. In the present invention, as the inert gas or the like, for example, argon gas, helium gas, nitrogen gas, or the like can be used.

In the present invention, the first, second, and further inorganic oxides such as silicon oxide formed by the above-described plasma chemical vapor deposition (CVD) method are used. The deposited film or the like is desirably a thin deposited film having a high flexibility and the like in order to prevent the occurrence of cracks and the like in the single-layer deposited film itself. Therefore, in the present invention, the characteristics of the deposited film formed by the above-mentioned plasma chemical vapor deposition method (CVD method) are the film forming speed, plasma power, and a monomer gas for vapor deposition such as an organic silicon compound. Although it is influenced by the composition ratio of the mixed gas composition for vapor deposition composed of oxygen gas, inert gas, and others, the film formation parameters such as the degree of vacuum in the vacuum chamber, etc., in the present invention, Especially,
When introducing a mixed gas composition for vapor deposition comprising a monomer gas for vapor deposition of an organic silicon compound or the like, an oxygen gas, an inert gas, or the like into a vacuum chamber through a raw material supply nozzle, the mixed gas composition for vapor deposition is used. By increasing the content of oxygen gas and lowering the content of the monomer gas for vapor deposition, the plasma power was further reduced, and plasma irradiation was performed under mild conditions, whereby the thin film was formed. , And has transparency, and is rich in flexibility,
It is also desirable to form a deposited thin film having excellent oxygen gas barrier properties and the like.

Further, in the present invention, in the above-mentioned plasma chemical vapor deposition method (CVD method), a mixed gas composition for vapor deposition comprising a monomer gas for vapor deposition of an organic silicon compound or the like, an oxygen gas, an inert gas, etc. Is introduced into the vacuum chamber through the raw material supply nozzle, when the content of the oxygen gas is increased and the content of the monomer gas for the deposition is reduced in the composition of the mixed gas composition for the deposition, the The ratio of the polar portion of the deposited film increases, and as a result, the adhesion between the base film and the deposited film, and further, the adhesion between the deposited films and the like are improved, and thus the adhesion is improved. By improving, the oxygen gas barrier property tends to be improved. Further, in the present invention, when the content of the oxygen gas is increased as described above, and the content of the monomer gas for deposition is reduced, and the plasma chemical vapor deposition is performed, a deposition film of an inorganic oxide such as silicon oxide is formed. In this case, the silicon oxide vapor-deposited film is composed of a silicon oxide vapor-deposited continuous thin film represented by the formula SiO _X , and furthermore, the value of X can be increased to form an extremely transparent vapor-deposited thin film. Is what you can do. Furthermore, in the present invention, the content of the oxygen gas is increased as described above, and the content of the monomer gas for vapor deposition is reduced, and the plasma chemical vapor deposition is performed. , The yellowing of the base film is suppressed, and as a result, the transparency of the transparent barrier film can be improved.

In the present invention, when performing the plasma chemical vapor deposition, the content of the oxygen gas in the mixed gas composition for vapor deposition containing at least a monomer gas for vapor deposition, an oxygen gas, and an inert gas is as follows. Specifically, in the composition of the mixed gas composition for vapor deposition, it is preferable that the composition be contained in a range of about 20% by volume or more. In the above, if the content is less than 20% by volume, it becomes difficult to obtain a vapor-deposited film having excellent oxygen gas barrier properties. Further, if the amount of oxygen gas is reduced, the base film tends to yellow, and in particular, oxygen Conversely, as the gas volume decreases,
It is not preferable because the content ratio of the monomer gas for vapor deposition or the inert gas increases, and the yellowing of the base film tends to increase remarkably. Further, in the present invention, when performing the plasma chemical vapor deposition, at least the vapor deposition monomer gas, oxygen gas, and the content of the vapor deposition monomer gas in the vapor deposition mixed gas composition containing an inert gas. Specifically, in the composition of the mixed gas composition for vapor deposition, it is preferable that the content be contained within a range of about 30% by volume or less. In the above, when the content of the vapor deposition monomer gas exceeds 30%, the concentration of the vapor deposition monomer gas in the mixed gas composition for vapor deposition increases, and the thickness of the deposited film formed increases. This is undesirable because the flexibility is reduced. Furthermore, a vacuum chamber
It is not preferable because a large amount of unreacted monomer gas for vapor deposition is present therein and lowers the degree of vacuum or is taken into the vapor-deposited film to lower its barrier property. In the present invention, as the mixed gas composition for vapor deposition,
The composition is such that at least a monomer gas for vapor deposition is 5
-30% by volume, oxygen gas in the range of 20-80% by volume, and other inert gas, if necessary,
It is preferable to use a mixed gas composition for vapor deposition containing other components.

Next, in the present invention, the above mixed gas composition for vapor deposition is introduced into a vacuum chamber through a raw material supply nozzle, and a vapor deposited film of an inorganic oxide such as silicon oxide is formed by glow discharge plasma. In this case, it is preferable to form a film. At this time, a current is supplied to the cooling / electrode drum from a power source arranged outside the chamber in a current value range of less than 14 kW, and plasma chemistry is performed under mild conditions. It is desirable to perform evaporation to produce a transparent barrier film having an inorganic oxide evaporation film. In the above, when the current value exceeds 14 kW, the conditions of plasma chemical vapor deposition become severe, for example, the base film receives the impact, causes yellowing or deterioration, and it is difficult to suppress the occurrence. In addition, since the plasma becomes unstable and the arcing phenomenon becomes very likely to occur, a large number of holes are apt to be formed in the base film having poor plasma resistance, and furthermore, the vapor deposition having excellent oxygen gas barrier properties and the like. This is not preferable because it tends to be difficult to form a film. In the present invention, specifically, it is preferable to supply a current within a range of a current value of about 6 to 14 kW. In the present invention, plasma deposition is performed in a range of about 50 to 150 m / min as a film forming speed and about 30 to 80 μbar as a degree of vacuum in a vacuum chamber, and each deposition film is formed. Into a film
It is preferred to layer or more layers.

In the present invention, the silicon oxide deposited film formed by the above-mentioned plasma chemical vapor deposition method is represented by the formula SiO _x (where X represents a number of 1 to 2). It is a continuous vapor-deposited thin film mainly composed of silicon oxide. Further, from the viewpoint of transparency and the like, the formula SiO _x (where X
Represents a number from 1.3 to 1.9. ) Is preferably a continuous thin film mainly composed of a deposited silicon oxide film. In addition, the above-described silicon oxide vapor-deposited film is made of a silicon oxide compound containing silicon and oxygen as constituent elements, and is further made of one or more kinds of trace constituent elements made of carbon, hydrogen, silicon, or oxygen. It is composed of a continuous vapor-deposited film of silicon oxide containing at least one compound. Further, the above silicon oxide deposited film is made of a silicon oxide compound containing silicon and oxygen as constituent elements,
Oxidation in which at least one compound comprising one or more elements of carbon, hydrogen, silicon, or oxygen is contained, and the compound decreases in the depth direction from the film surface It is made of a continuous vapor deposition film of silicon.
Furthermore, when the silicon oxide vapor-deposited film contains a compound made of carbon, the content of carbon is reduced in the depth direction of the film thickness. Thus, the film structure of the deposited film as described above is, for example,
X-ray photoelectron spectroscopy (Xray Photoselect)
ron Spectroscopy (XPS), Secondary Ion Mass Spectrometer (Secondary Ion Ma)
This can be confirmed by analyzing the deposited film using a method of performing analysis by ion etching in the depth direction using a surface analyzer such as ss spectroscopy (SIMS). In the present invention, the thickness of the deposited film of the inorganic oxide such as silicon oxide can be formed in the range of about 50 to 2000 °. However, in the present invention,
The first, second, and further vapor-deposited films of inorganic oxides such as silicon oxide are thin films, and it is desirable that they have a film quality that breaks down into flexibility and the like. Is about 50 to 500 °, preferably about 50 to 300 °. In the above, the film thickness is 300 °, 500 °, 1000 °, and 2000
If it exceeds Å, the flexibility of the deposited film tends to be inferior, and it is not preferable because cracks and the like tend to be easily generated, and if the film thickness is less than 50 °, oxygen gas barrier properties, This is not preferred because it tends to be inferior in water vapor barrier properties.

Next, in the present invention, the heat-sealing resin forming the heat-sealing resin layer constituting the laminate using the transparent barrier film according to the present invention is heat-meltable. And resin films or sheets that can be fused to each other, and specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene , Polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene Polyolefin such as propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene Modified polyolefin resin obtained by modifying an unsaturated resin such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc., polyvinyl acetate resin, poly (meth) acrylic resin Resins, polyvinyl chloride resins, and other resin films or sheets can be used. Thus, the above-mentioned film or sheet can be used in the form of a coating film made of a composition containing the resin. The thickness of the film, film or sheet is preferably about 5 μm to 300 μm, and more preferably about 10 μm to 100 μm.

In the present invention, the laminate according to the present invention may be, for example, a film of various resins, a paper base, a metal material, or a synthetic resin in addition to the heat-sealing resin layer as described above. It is possible to manufacture various laminates by arbitrarily combining with packaging materials such as paper, cellophane, etc. that constitute packaging containers, and to manufacture packaging materials suitable for filling and packaging various articles. is there. As the resin film, 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, acid-modified polyolefin resin, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, poly Vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer A polymer (ABS resin), a polyester resin, a polyamide resin, a polycarbonate resin, a polyvinyl alcohol resin, a saponified ethylene-vinyl acetate copolymer, a fluorine resin,
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 can be used in 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. Further, in the above, as the paper substrate, for example, a paper substrate such as a strongly sized bleached or unbleached paper, a paper substrate such as pure white roll paper, kraft paper, paperboard, or processed paper, or the like is used. can do. 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 . In the above description, as the metal material, for example, an aluminum foil, a resin film having an aluminum vapor-deposited film, or the like can be used.

Next, a method of manufacturing a laminate using the above-mentioned materials in the present invention will be described.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pre-treatment such as a corona treatment, an ozone treatment, a framing treatment, or the like can be performed on the film. Anchor coating agents such as polyester, isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate And known adhesives such as adhesives for laminates such as cellulose, cellulose, etc.
Coating agents, adhesives and the like can be used.

Next, in the present invention, a method for producing a bag or a box using the above-mentioned laminate 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 body manufactured by such a method, the heat-sealing resin layer of the inner layer is opposed to the laminated body, and the heat-sealing resin layer is folded, or the two sheets are overlapped, and the peripheral end portion is further folded. A bag can be formed by providing a seal portion by heat sealing. Thus, as a bag making method, the above-mentioned laminate 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)
Can also be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-described composite film. 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 laminate in which a paper substrate is laminated is produced as a laminate, 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 produced as described above is excellent in transparency, gas barrier properties against oxygen, water vapor, etc., impact resistance, and the like.
Having post-processing suitability such as printing, bag making or box making,
In addition, it prevents peeling of the deposited film as a barrier film, and prevents the occurrence of thermal cracks, and also prevents its deterioration, thereby exhibiting excellent resistance as a barrier film. It has excellent suitability for packing and preservation of various articles such as chemicals or cosmetics such as products, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives and adhesives, and others.

[0025]

The present invention will be described more specifically with reference to the following examples. Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was divided into two vacuum chambers.
The biaxially stretched polyethylene terephthalate is mounted on a delivery roll of a plasma chemical vapor deposition apparatus having a
A transparent barrier film according to the present invention was produced by laminating two layers of first and second silicon oxide vapor-deposited films on the same film under the following conditions. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 2.
8: 3.3 (unit: slm, standard drier)
Minute, standard litter minu
te, the same shall apply hereinafter) Degree of vacuum in vacuum chamber; 55 μbar Number of vacuum chambers; 2 Power of cooling / electrode drum; 12 kW Film transport speed; 120 m / min Film layer: 2 layers Thickness of each deposited film: 70 ° ( (Two layers have the same thickness.) (2). Next, the above-prepared transparent barrier film was used and mounted on one of the delivery rolls of a dry laminator coater, and an adhesive layer was formed on the second silicon oxide deposited film surface. On the other hand, a non-stretched polypropylene film having a thickness of 40 μm, which is a sealant film, is used, and is mounted on the other delivery roll. Then, both are dry-laminated under the following conditions. A laminate according to the present invention was manufactured. (Adhesive layer); Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd.) (Trade name, A-50) (mixing ratio) base material: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry)

Embodiment 2 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was divided into two vacuum chambers.
The biaxially stretched polyethylene terephthalate is mounted on a delivery roll of a plasma chemical vapor deposition apparatus having a
A transparent barrier film according to the present invention was produced by laminating two layers of first and second silicon oxide vapor-deposited films on the same film under the following conditions. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 0.6: 5.
5: 2.4 (unit: slm) Degree of vacuum in vacuum chamber; 55 μbar Number of vacuum chambers; 2 Power of cooling / electrode drum; 12 kW Film transport speed; 120 m / min Film layer: 2 layers Film thickness: 70 ° (both layers have the same thickness) (2). Next, the above-prepared transparent barrier film was used and mounted on one of the delivery rolls of a dry laminator coater, and an adhesive layer was formed on the second silicon oxide deposited film surface. On the other hand, a non-stretched polypropylene film having a thickness of 40 μm, which is a sealant film, is used, and is mounted on the other delivery roll. Then, both are dry-laminated under the following conditions. A laminate according to the present invention was manufactured. (Adhesive layer); Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd.) (Trade name, A-50) (mixing ratio) base material: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry)

Comparative Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was divided into two vacuum chambers.
The biaxially stretched polyethylene terephthalate is mounted on a delivery roll of a plasma chemical vapor deposition apparatus having a
On the film, two layers of first and second silicon oxide vapor-deposited films were formed under the following conditions to form a film, thereby producing a transparent barrier film. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 0.5: 1.
8: 1.8 (unit: slm) Degree of vacuum in vacuum chamber; 20 μbar Number of vacuum chambers: 2 Power of cooling / electrode drum; 5 kW Film transport speed; 40 m / min Film layer: 2 layers Film thickness: 160 ° (both layers have the same thickness) (2). Next, the above-prepared transparent barrier film was used and mounted on one of the delivery rolls of a dry laminator coater, and an adhesive layer was formed on the second silicon oxide deposited film surface. On the other hand, a non-stretched polypropylene film having a thickness of 40 μm, which is a sealant film, is used, and is mounted on the other delivery roll. Then, both are dry-laminated under the following conditions. A laminate was manufactured. (Adhesive layer); Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd.) (Trade name, A-50) (mixing ratio) base material: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry)

Comparative Example 2 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was divided into two vacuum chambers.
The biaxially stretched polyethylene terephthalate is mounted on a delivery roll of a plasma chemical vapor deposition apparatus having a
On the film, two layers of first and second silicon oxide vapor-deposited films were formed under the following conditions to form a film, thereby producing a transparent barrier film. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.6: 5.
0: 5.0 (unit: slm) Degree of vacuum in vacuum chamber; 90 μbar Number of vacuum chambers: 2 Cooling / electrode drum power; 15 kW Film transport speed; 160 m / min Film layer: 2 layers Film thickness: 20 ° (both layers have the same thickness) (2). Next, the above-prepared transparent barrier film was used and mounted on one of the delivery rolls of a dry laminator coater, and an adhesive layer was formed on the second silicon oxide deposited film surface. On the other hand, a non-stretched polypropylene film having a thickness of 40 μm, which is a sealant film, is used, and is mounted on the other delivery roll. Then, both are dry-laminated under the following conditions. A laminate was manufactured. (Adhesive layer); Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd.) (Trade name, A-50) (mixing ratio) base material: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry)

Comparative Example 3 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was placed in one vacuum chamber.
A biaxially stretched polyethylene terephthalate film is mounted on a delivery roll of a plasma chemical vapor deposition apparatus having Was manufactured. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 2.
8: 3.3 (unit: slm) Degree of vacuum in vacuum chamber; 55 μbar Number of vacuum chambers: Number of cooling / electrode drum power; 12 kW Film transport speed; 60 m / min Film layer: 1 layer Film thickness: 140 ° (both layers have the same thickness) (2). Next, the above-prepared transparent barrier film was used and mounted on one of the delivery rolls of a dry laminator coater, and an adhesive layer was formed on the second silicon oxide deposited film surface. On the other hand, a non-stretched polypropylene film having a thickness of 40 μm, which is a sealant film, is used, and is mounted on the other delivery roll. Then, both are dry-laminated under the following conditions. A laminate was manufactured. (Adhesive layer); Use urethane-based adhesive (Main agent) Urethane-based (Takeda A-515, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd.) (Trade name, A-50) (mixing ratio) base material: curing agent = 10: 1 (solvent) ethyl acetate (coating amount) 4.0 g / m ² (dry)

Experimental Example 1 The following data was measured for each of the transparent barrier films and the laminates manufactured in Examples 1 and 2 and Comparative Examples 1 to 3 above. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is 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 oxygen permeability and water vapor permeability after 4% pull This is for a laminate, after aging, pulling a 15 mm wide one with tensilon, and in the same manner as above,
Oxygen permeability and water vapor permeability were measured. The above measurement results are shown in Table 1 below.

[0031]

[Table 1] Measurement of oxygen permeability and water vapor permeability In Table 1 above, the oxygen permeability is cc / m ² / da
The unit is y · 23 ° C. · 90% RH, and the water vapor permeability is the unit of g / m ² / day · 40 ° C. · 100% RH.

As is clear from the above measurement results, those of Examples 1 and 2 are excellent in oxygen gas barrier properties, water vapor barrier properties and the like in the transparent barrier films and laminates. 3 was much better than that. On the other hand, all of Comparative Examples 1 to 3 were inferior.

[0033]

As is apparent from the above description, the present invention provides a method for forming an inorganic oxide film such as silicon oxide on one surface of a substrate film by a plasma chemical vapor deposition method. Focusing on providing two or more layers of deposited films of the product, first, on one surface of the base film, a first inorganic oxide deposited film is formed by plasma enhanced chemical vapor deposition, Next, on the first inorganic oxide vapor-deposited film, a second inorganic oxide vapor-deposited film is formed by plasma-enhanced chemical vapor deposition in exactly the same manner as described above. A transparent barrier film is manufactured by laminating three or more layers of a vapor-deposited film of an inorganic oxide by a chemical vapor deposition method, and thus the inorganic oxide film finally formed into the transparent barrier film is formed. At least heat sealability on the surface of the deposited film Laminating a fat film to produce a laminate, using the laminate, making a bag to produce a packaging container, and filling the content into the packaging container to produce a packaged product It has excellent transparency and high gas barrier properties against oxygen gas, water vapor, etc., and is suitable for, for example, filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, detergents, etc. It is possible to produce a transparent barrier film which is useful for producing a film and the like, and a laminate using the same.

[Brief description of the drawings]

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

FIG. 2 is a schematic cross-sectional view schematically showing a layer configuration of another example of the transparent barrier film according to the present invention.

FIG. 3 is a schematic cross-sectional view showing the outline of the function and effect of the transparent barrier film according to the present invention.

FIG. 4 is a schematic cross-sectional view schematically showing a layer configuration of an example of a laminate using the transparent barrier film according to the present invention.

FIG. 5 is a schematic structural view showing an outline of a plasma chemical vapor deposition apparatus for a method for producing a transparent barrier film according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent barrier film 1a Transparent barrier film 2 Substrate film 3a Inorganic oxide field vapor deposition film, such as 1st silicon oxide, etc. 3b Inorganic oxide field vapor deposition film, such as 1st silicon oxide, etc. 4a Crack 4b Crack 5 Heat stress Rolling resin layer 11 Laminated body 31 Plasma chemical vapor deposition device 32 First vacuum chamber 33 Unwinding roll 34 Auxiliary roll 35 Cooling / electrode drum 36 Gas supply device 37 Gas supply device 38 Raw material volatile supply device 39 Material supply nozzle 40 Glow discharge plasma 41 Power supply 42 Magnet 43 Auxiliary roll 44 Auxiliary roll 45 Second vacuum chamber 46 Auxiliary roll 47 Auxiliary roll 48 Cooling / electrode drum 49 Gas supply device 50 Gas Supply device 51 Raw material supply device 52 Raw material supply nozzle 53 Glow discharge plasma 54 Power supply 56 Magnet G 57 Take-up roll 58 Vacuum pump 59 Vacuum pump

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B65D 81/24 B65D 81/24 D C23C 16/40 C23C 16/40

Claims (6)

[Claims] 1. A transparent barrier film comprising two or more inorganic oxide deposited films formed by plasma enhanced chemical vapor deposition on one surface of a substrate film. 2. The transparent barrier film according to claim 1, wherein the base film comprises a biaxially oriented polyethylene terephthalate film or a biaxially oriented nylon film. 3. The transparent barrier film according to claim 1, wherein the inorganic oxide deposited film comprises a silicon oxide deposited film. 4. An inorganic oxide deposited film comprising a silicon oxide compound, and further comprising carbon, hydrogen, silicon or oxygen.
At least one compound consisting of one or more elements
4. The transparent barrier film according to claim 1, comprising a continuous vapor-deposited film containing at least one species. 5. An inorganic oxide deposited film comprising a silicon oxide compound, and further comprising carbon, hydrogen, silicon or oxygen.
At least one compound consisting of one or more elements
5. The transparent film according to claim 1, wherein the compound comprises a continuous vapor-deposited film containing at least one species and decreasing in depth from the film surface. Barrier film. 6. On one surface of a substrate film, a vapor-deposited inorganic oxide film formed by plasma-enhanced chemical vapor deposition is laminated on two or more layers to form a transparent barrier film with an inorganic oxide vapor-deposited film. A laminate comprising at least a heat-sealing resin layer.