JP2000355071A - Barrier film, laminated material using the film, and method and device for manufacturing barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the barrier film having high barrier properties to oxygen gas, water vapor or the like and excellent in transparency, and make it possible to use for the filling and packaging of various articles by providing a thin inorganic oxide film produced by a plasma chemical film making method on one side of a polyamide- based resin film, the water content of which is removed through the irradiation of heat rays. SOLUTION: On one side of a polyamide-based resin film 1, the water content of which is removed through the irradiation of heat rays, a thin inorganic oxide film 2 made of silicon oxide or the like produced by a plasma chemical film making method with a low temperature plasma generating device or the like through the application of a mixed gas composition consisting mainly of a film forming monomer gas of an organic silicon compound or the like and including inert gas such as oxygen gas, argon gas, helium gas or the like is provided. As the low temperature plasma generating device, a generating device of high frequency plasma, pulse wave plasma, microwave plasma or the like is employed. As a result, the resultant film has barrier properties to oxygen gas, water vapor or the like, is excellent in transparency and useful for the filling and packaging of various articles such as eatable and drinkable articles, medicines or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barrier film, a laminated material using the same, and a method and apparatus for producing a barrier film. More specifically, the present invention relates to transparency, gas barrier properties against oxygen gas or water vapor, and the like. Excellent, furthermore, having a laminating suitability, for example, a barrier film excellent in filling and packaging suitability for various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, etc., a laminate material using the same, and a barrier film The present invention relates to a method and an apparatus for producing the same.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals and others. Among them, in recent years, silicon oxide, aluminum oxide, magnesium oxide, and others have been used as a barrier material against oxygen gas or water vapor on the surface of a plastic substrate such as a polyester resin film or a polyamide resin film. Physical vapor deposition (PVD) such as vacuum deposition, sputtering, and ion plating, or plasma chemical vapor deposition, thermochemical vapor deposition, or photochemical vapor. A barrier film formed by forming a vapor-deposited film of an inorganic oxide by using a chemical vapor deposition method (CVD method) such as a phase growth method has attracted attention. Thus, the above barrier film is arbitrarily laminated with other plastic films, paper base materials, other materials, etc. to form various laminated materials, and is useful for packing and packing various articles. The manufacture of containers is expected to increase the demand in the future. In particular, the above barrier film is superior to a barrier material such as a conventional aluminum foil or a polyvinylidene chloride-based resin coat film in terms of appropriateness for incineration disposal treatment, and various excellent materials suitable for environmental protection. It has advantages and is a material of interest.

[0003]

In the above-mentioned barrier film, the polyamide resin film as the base film also has a higher water absorption than the polyester resin film as the base film. Is very high. Usually, a polyester-based resin film hardly absorbs moisture, but a polyamide-based resin film has a problem that the saturated water absorption reaches about 4% in an environment of a relative humidity of 60%. Thus, when forming a barrier film as described above, when forming a film using a polyamide resin film having a high water absorption as described above as a substrate film, the polyamide film in a vacuum oven Moisture floats from the base resin film, which causes a problem that the degree of vacuum in the vacuum pot is reduced, and it becomes difficult to produce a barrier film having excellent gas barrier properties against oxygen gas, water vapor and the like. Further, as described above, when moisture or the like floats on the surface of the polyamide-based resin film as the base film, moisture is generated between the film-forming drum and the polyamide-based resin film as the base film. The polyamide resin film floats on the membrane drum, or wrinkles or the like are generated in the polyamide resin film. Due to this, a barrier having excellent gas barrier properties against oxygen gas, water vapor, etc., as described above. There is a problem that it becomes difficult to produce a conductive film. Furthermore, as described above, when water or the like floats on the surface of the polyamide-based resin film, and the degree of vacuum or the like decreases, the above-described floated moisture or the like during film formation may be, for example, silicon oxide. Into the deposited film, which affects the characteristics of the deposited film of silicon oxide, and leads to a problem that the obtained barrier film has a reduced gas barrier property against oxygen gas, water vapor and the like. Further, when the polyamide resin film floats on the film forming drum as described above, or when wrinkles or the like are generated in the polyamide resin film, the plasma during film formation becomes unstable, so-called heat loss. This causes a problem that the resulting barrier film has a reduced gas barrier property against oxygen gas, water vapor and the like. For this reason, in the above-mentioned barrier film, in order to improve the gas barrier properties against oxygen gas or water vapor, for example, on the surface of a polyamide-based resin film as a base film, in advance, a corona discharge treatment,
Roughening the surface by performing a pre-treatment such as glow discharge treatment, or, in advance, forming an anchor coating agent layer by coating an anchor coating agent for vapor deposition such as urethane-based or ester-based, and forming a base film. As a method of improving the gas barrier properties by improving the adhesion between the polyamide resin film and the vapor-deposited film, etc., has been proposed, but the effect thereof can be expected to some extent, but it is still insufficient. In fact, it is difficult to produce a barrier film having a high barrier property that can satisfy the requirements described above. There is a problem of increasing costs. For example, using a polyurethane-based organic anchor coating agent, coating it on the surface of a polyamide-based resin film in advance to form an anchor coating agent layer, and then, through the anchor coating agent layer, an inorganic oxide When a vapor-deposited film is formed, the degree of vacuum during vapor deposition is reduced due to residual solvents and the like contained in the anchor coat agent layer, and further, because the anchor coat agent layer itself is soft, the However, it is extremely difficult to form a vapor deposition film as desired, and it is extremely difficult to form a vapor deposition film as desired. As a result, it is not possible to produce a barrier packaging material having excellent gas barrier properties against oxygen gas or water vapor. It is a fact. In addition, as a method of manufacturing a barrier film for forming a barrier layer on these base films, the base material is wound around a film forming drum provided in a vacuum oven, and the film forming drum is rotated to form the base material. While running continuously, the raw material gas is supplied near the outer periphery of the film forming drum while the raw material gas is supplied near the outer periphery of the film forming drum while the raw material gas is supplied near the outer periphery of the film forming drum. Causing a plasma discharge in the vicinity,
Thus, a method of continuously forming a barrier layer on the surface of a running base material is known (for example, Japanese Patent Application Laid-Open No. 8-1422).
No. 52). According to the above-described manufacturing method, film formation can be performed continuously, so that a barrier film can be efficiently manufactured at low cost. However, a phenomenon that affects the quality of the film may occur, such as wrinkling of the film during film formation and instability of the plasma. Phenomena that adversely affect the quality of such a film, not only polyamide-based resin film, polypropylene-based resin film that absorbs moisture similarly to polyamide-based resin film, polyethylene terephthalate-based resin film, etc. Occurred as well. Therefore, the present invention has a high barrier property against oxygen gas or water vapor,
And, excellent in transparency, for example, foods and drinks, pharmaceuticals, cosmetics, chemicals, a barrier film useful for filling and packaging various articles such as other and a laminate using the same,
It is another object of the present invention to provide a method and an apparatus for producing a barrier film capable of improving the stability of the quality of the barrier film.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has found that a polyamide resin film is irradiated with heat rays to remove moisture and is relatively flexible. Focus on thin films by plasma chemical film deposition method, which is rich in properties, follow-up properties, can suppress the occurrence of cracks, etc., and hardly degrades barrier properties, first use an infrared lamp, etc., The resin film is irradiated with heat rays from the above-mentioned infrared lamp to remove moisture contained in the polyamide resin film, and then, on one surface of the polyamide resin film, silicon oxide is formed by a plasma chemical film formation method. A barrier film is manufactured by providing a thin film of an inorganic oxide such as the above, and further, at least a heat-sealing resin layer or the like is provided on the thin film surface of the inorganic oxide of the barrier film. Then, the laminated material is used, and then the laminated material is used to form a bag to produce a packaging container. Thereafter, the contents are filled and packaged in the packaging container, and the opening is further heated. When the package was manufactured by sealing, when a thin film of an inorganic oxide such as silicon oxide was formed, a phenomenon in which moisture and the like emerged from the polyamide resin film was hardly recognized, and the polyamide was not affected by the phenomenon. A thin film of an inorganic oxide such as silicon oxide can be formed on the surface of a resin-based resin film very well, and excellent adhesion between the polyamide resin film and a thin film of an inorganic oxide such as silicon oxide can be obtained. As a result, it has an extremely high barrier property against oxygen gas or water vapor, and has excellent transparency,
Excellent laminating strength, for example, food and drink, pharmaceuticals,
The present invention has been completed by finding that a barrier film useful for filling and packaging various articles such as cosmetics, chemicals, and the like and a laminated material using the same can be produced.

That is, the present invention is characterized in that a thin film of an inorganic oxide is provided on one surface of a polyamide resin film from which moisture contained has been removed by irradiation with heat rays by a plasma chemical film formation method.

[0006] In the process of forming a barrier film, the inventors have obtained the following knowledge. Plasma CVD on the surface of the substrate while keeping the film forming drum and substrate in close contact
When the film is formed, the substrate is heated by the heat of the plasma generation region, moisture in the substrate evaporates, and a gas such as water vapor is released from the substrate. Since the substrate and the film forming drum are in close contact with each other, when gas is released from the side of the substrate that is in contact with the film forming drum, the gas expands the substrate and lifts up from the film forming drum. And the quality of the film is deteriorated. The film forming drum is cooled to room temperature or lower in order to suppress the heating of the substrate by the plasma. However, if the substrate rises from the drum, the cooling effect of the film forming drum is also impaired, and the quality of the film is impaired in this respect as well.

If the moisture in the substrate evaporates during the film forming process and causes a problem, the moisture is released to the back surface (the surface in close contact with the film forming drum) of the substrate in the pretreatment before the film formation. What is necessary is just to perform the process of suppressing. That is, the present invention provides a method for producing a barrier film, comprising: performing a pretreatment for suppressing the release of moisture on the back surface of a film-shaped substrate; and forming a barrier layer on the surface of the substrate. Has solved the above-mentioned problem.

According to the present invention, since the pretreatment before the film formation is performed to suppress the release of water to the back surface of the base material, the water does not evaporate from the base material at the time of film formation. The quality of the film and the like is kept high.

[0009] The moisture in the substrate includes water contained in the substrate and adsorbed water adsorbed on the surface of the substrate. If the moisture in the base material evaporates in the film forming step and causes a problem, the moisture in the base material may be removed by a pretreatment before the film formation. That is, the present invention relates to a method for producing a barrier film, wherein a barrier layer is formed by a plasma chemical film formation method on the surface of the substrate while the film-shaped substrate is continuously running, while the substrate is running. The above-described problem has been solved by performing a pretreatment for removing moisture from the base material before forming the barrier layer. For example, in the case of a polyamide-based resin film, the moisture content of the base material is 0.2 to 1.0%,
Desirably, about 0.3 to 0.5%, and in the case of a polyester resin film, the water content of the substrate is 0.02% to
0.2%, preferably about 0.05% to 0.1%.

According to the present invention, since the moisture in the base material is removed by the pretreatment before the film formation, the quality of the film formation and the like can be maintained at a high level without evaporating the water from the base material during the film formation. You.

The pretreatment for suppressing the release of moisture from the back surface of the base material and the pretreatment for removing moisture from the base material include heating the base material, evaporating the moisture in the base material, and moving the base material to the outside. A method or a method of modifying the back surface of the base material can be adopted.

In order to prevent the gas from being released from the side of the substrate in close contact with the film forming drum, it is desirable to heat the rear surface of the substrate. Here, the moving base material may be heated by irradiating it with heat rays, may be heated by contacting a heating body with the base material, or may be heated by applying a high-frequency electromagnetic field to the base material. Alternatively, the substrate may be irradiated with an electron beam and heated.

The modification of the back surface of the substrate refers to a process of crushing the voids on the back surface of the substrate so as to limit the evaporation of water from the back surface of the substrate. And melting the surface layer on the back surface to prevent moisture inside the substrate from going outside. This modification includes:
Flame treatment (flame treatment), corona treatment, hot air treatment, glow discharge plasma treatment using vacuum, or the like can be used.

Further, the present invention provides a pretreatment means for performing a pretreatment for suppressing the release of moisture on the back surface of a film-like base material, and a film formation means for forming a barrier layer on the surface of the base material. It can also be configured as a barrier film manufacturing apparatus characterized by comprising a, while continuously running a film-like substrate, a barrier layer by a plasma chemical film forming method on the surface of the running substrate In the apparatus for producing a barrier film to be formed, a pretreatment means for removing moisture from the substrate before forming the barrier layer may be provided.

Here, as the pretreatment means, a heating device for heating the substrate, or a device for modifying the back surface of the substrate by plasma treatment or corona treatment can be used.

According to this manufacturing apparatus, for the same reason as in the above-described manufacturing method, the quality of film formation and the like can be maintained at a high level without moisture evaporating from the substrate during film formation.

Further, the barrier film according to the present invention is characterized in that a barrier layer is formed on the surface of a film-like base material which has been subjected to a pretreatment for suppressing the release of moisture on the back surface.

In this film, since the base material does not rise from the drum during the production for the above-mentioned reason, the barrier layer is formed with a high quality, and a highly reliable barrier effect is exhibited.

Further, the barrier film according to the present invention comprises:
A barrier layer is formed on one surface of a film-shaped substrate from which moisture contained by heating is removed by a plasma chemical film formation method.

This film also has a barrier layer of high quality because the base material does not rise from the drum during the production for the reasons described above, and exhibits a highly reliable barrier effect.

Further, the barrier film according to the present invention is characterized in that a barrier layer is formed on the surface of a film-like base material whose back surface is modified by a plasma chemical film forming method.

This film also has a high quality barrier layer because the substrate does not rise from the drum during the production for the reasons described above, and exhibits a highly reliable barrier effect.

As the base material, not only a polyamide resin film having a high water content but also various resin films such as a polypropylene resin film and a polyethylene terephthalate resin film having a low water content can be used.
Of course, the substrate is not limited to packaging.

[0024]

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

First, the barrier film A according to the present invention
As shown in FIG. 1, an inorganic oxide thin film 2 was provided on one surface of a polyamide-based resin film 1 as a substrate from which moisture contained therein was removed by irradiation with heat rays by a plasma chemical film formation method. It has a configuration. Thus, as the laminate B using the barrier film according to the present invention,
As shown in FIG. 2, the polyamide-based resin film 1 from which heat rays are irradiated to remove moisture contained as described above is provided with an inorganic oxide thin film 2 by plasma chemical film formation on one surface. If necessary, at least a heat-sealable resin layer is provided on the surface of the inorganic oxide thin film 2 of the barrier film A via, for example, an adhesive layer for lamination or an anchor coat agent layer (not shown). 3 is provided. In addition, the above illustration is an example of the example, and the present invention is not limited to the example.

The method for producing the barrier film according to the present invention as described above will now be described. The barrier film according to the present invention is, for example, a film-forming monomer such as an organosilicon compound. A gas mixture is used as a raw material, and a mixed gas composition for film formation containing an oxygen gas, an inert gas such as an argon gas and a helium gas, and the like is further adjusted. And a method of forming a thin film of an inorganic oxide such as silicon oxide by a plasma chemical film formation method (CVD method) using a low-temperature plasma generator or the like.
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.

In the present invention, an example of a method for producing a barrier film according to the present invention utilizing the above-described method of forming a thin film of an inorganic oxide by a plasma chemical film forming method will be described. FIG. 3 is a schematic configuration diagram of a plasma chemical film forming apparatus showing an outline of a method of forming a thin film of an inorganic oxide by a plasma chemical film forming method according to the present invention.

In the present invention, as shown in FIG. 3, first, the polyamide resin film 1 is unwound from an unwinding roll 13 disposed in a vacuum chamber 12 of a plasma chemical film forming apparatus 11. Thus, in the present invention,
For example, infrared lamps 17 and 18 are arranged between and above the guide rolls 14 and 15, and heat rays generated by the infrared lamps 17 and 18 are applied to both surfaces of the polyamide resin film 1. Irradiation removes moisture contained in the polyamide resin film 1 in advance. Next, the polyamide-based resin film 1 unwound from the unwinding roll is transferred to the guide rolls 14 and 15.
Through a cooling / electrode drum at a predetermined speed. The film forming drum 16 is connected to a power supply, and the vacuum chamber 12 is grounded. The film forming drum 16 is cooled to a room temperature or lower (for example, −10 to 0 ° C.) by a cooling device (not shown). Film forming drum 16
Is set such that the temperature of the polyamide-based resin film 1 during film formation does not rise above its glass transition temperature. The surface of the film forming drum 16 is formed smooth by, for example, chrome plating. Next, in the present invention, while continuously running the polyamide resin film 1 using a film forming means such as the film forming drum 16, the surface of the running polyamide resin film 1 is formed by a plasma chemical film forming method. A barrier layer is formed. Gas supply device 19, 2
O, and oxygen gas, an inert gas, a monomer gas for film formation such as an organic silicon compound, and the like are supplied from the raw material volatilization supply device 21 and the like, and a mixed gas composition for film formation composed thereof is adjusted. The above-mentioned mixed gas composition for film formation is introduced into the vacuum chamber 12 through the raw material supply nozzle 22, and the surface of the polyamide resin film 1 conveyed on the peripheral surface of the film formation drum 16 is Plasma is generated by the glow discharge plasma 23 and irradiated with the plasma to form a thin film of an inorganic oxide such as silicon oxide as a barrier layer. In the present invention, at this time, the film forming drum 16 composed of the cooling / electrode drum is placed in the vacuum chamber 12
A predetermined electric power is applied from a power supply 24 disposed outside, and the cooling / electrode drum 1
In the vicinity of 6, a magnet 25 is arranged to promote the generation of plasma. Next, in the present invention, the polyamide-based resin film 1 on which the thin film of the inorganic oxide such as silicon oxide is formed is wound around the winding roll 26 via the guide rolls 15 ′ and 14 ′. It can produce a barrier film. In the drawing, reference numeral 27 denotes a vacuum pump. During film formation, the inside of the vacuum chamber 12 is reduced to a predetermined pressure by the vacuum pump 27. The pressure is set to a range in which plasma can be generated, and is generally 1.3332 to 13.3322 Pa.
(10-100 mmtorr), preferably 6.666
It is set to 1 Pa (50 mmtorr). The above exemplification is an example of the method for producing a barrier film according to the present invention, and it is needless to say that the present invention is not limited thereby.

In the above-mentioned method for producing a barrier film according to the present invention, an infrared lamp or the like is used in-line with a line for forming a thin film of an inorganic oxide such as silicon oxide, and its heat rays are irradiated. Although the moisture contained in the polyamide-based resin film has been removed in advance, in the present invention, of course, an infrared lamp or the like is used in advance in the off-line of a film forming line of a thin film of an inorganic oxide such as silicon oxide, By irradiating the heat rays, moisture contained in the polyamide-based resin film is removed in advance, and thereafter, the inorganic oxide such as silicon oxide is formed on a thin film forming line of the inorganic oxide such as silicon oxide as described above. It is also possible to produce a barrier film according to the present invention by forming a thin film. In the present invention, it is preferable to use an infrared lamp of about 300 to 2,000 W, preferably about 500 to 1000 W, as the infrared lamp for irradiating the heat rays. In the present invention,
As means for irradiating heat rays, in addition to the infrared lamp as described above, for example, a means such as a ceramic heater is used to irradiate the polyamide-based resin film with heat rays to remove water contained in the polyamide-based resin film. Can be removed in advance. In the present invention, when the polyamide resin film is irradiated with heat rays to remove water in advance as described above, an infrared lamp to be used and irradiation time (film formation of a polyamide resin film for forming a thin film of an inorganic oxide) are used. For example, when the infrared lamp is about 500 W and the irradiation time is about 0.5 seconds, the moisture content of the polyamide-based resin film is initially When the moisture content of about 3% is removed by irradiating it with heat rays, the moisture content of the moisture contained in the polyamide resin film can be reduced to about 0.3%. Thus, in the present invention, when a thin film of an inorganic oxide such as silicon oxide is formed by the above-described plasma chemical film forming method, the content of moisture in the polyamide resin film is determined by irradiating heat rays. It is preferable that the moisture content is adjusted to about 0.1 to 1.5% to form a film. The above moisture content can be measured by a Karl Fischer method or the like.

In the present invention, when the inorganic oxide formed by the above-mentioned plasma chemical film formation method is silicon oxide, its thin film is represented by the formula SiOx (where X is
Is a continuous thin film mainly composed of silicon oxide represented by formula (1) or (2), and further, from the viewpoint of transparency and the like, the formula S
iOx (where X represents a number from 1.3 to 1.9)
Is preferably a continuous thin film mainly composed of silicon oxide represented by

The silicon oxide thin film is made of a silicon oxide compound containing silicon and oxygen as constituent elements, and one or more kinds of trace constituent elements consisting of carbon, hydrogen, silicon or oxygen. And a continuous thin film of silicon oxide containing at least one compound of the following formula: Further, the thin film of silicon oxide is made of a silicon oxide compound containing silicon and oxygen as constituent elements, and further contains at least one compound made of one or more elements of carbon, hydrogen, silicon, or oxygen. Containing more than one species, and wherein the compound is in the depth direction from the film surface,
It consists of a continuous thin film of silicon oxide whose content has been reduced. Furthermore, when the silicon oxide thin film contains a compound made of carbon, the feature is that the carbon content decreases in the depth direction of the film thickness. Thus, the film structure of the thin film as described above is
Regarding the silicon oxide thin film formed by the above-described plasma chemical film formation method, for example, an X-ray photoelectron spectrometer (Xray Photo)
oelectron Spectroscopy, XP
S), secondary ion mass spectrometer (Secondary)
Ion Mass Spectroscopy, SIM
This can be confirmed by performing elemental analysis of the thin film surface of silicon oxide using a method of performing analysis by ion etching in the depth direction using a surface analyzer such as S). In the present invention, the thickness of the thin 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 thin film of an inorganic oxide such as silicon oxide is a thin film, and it is desirable that the thin film has a high flexibility and the like. It is desirable that the angle is about 300 °, more preferably about 100 ° to 250 °. In the above description, when the film thickness exceeds 250 °, 300 °, and 2000 ° or the like, the flexibility and the like of the thin film tend to be inferior, and cracks and the like tend to be easily generated. If the thickness is less than 50 ° or even less than 100 °, it tends to be inferior in oxygen gas barrier properties, water vapor barrier properties, and the like, which is not preferable.

In the present invention, in the method for forming a thin film of an inorganic oxide such as silicon oxide by the plasma chemical film forming method according to the present invention, the film forming monomer gas constituting the film forming mixed gas composition may be used. Examples of the organic silicon compound include, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organosilicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in handling properties and forming a thin film. From the viewpoint of characteristics and the like, it is a particularly preferred original family. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the above-mentioned present invention, the polyamide resin film constituting the barrier film and the laminated material according to the present invention is, for example, excellent in impact resistance, piercing resistance, etc., and is rich in toughness. Any polyamide-based resin film or sheet that can hold a thin film of an inorganic oxide can be used.

Specifically, for example, nylon 46, nylon 6, nylon 66, nylon 610, nylon 61
2, films or sheets of various polyamide resins (nylon) such as nylon 7, nylon 11, nylon 12, and others can be used. The polyamide resin (nylon) film or sheet is, for example, a single layer or a film formed by co-extrusion of two or more layers, and further, for example, a tenter method or a tutenter method. Alternatively, it is desirable to use a film or sheet of a biaxially stretched polyamide resin (nylon) which has been stretched in a biaxial direction by a normal biaxial stretching method such as a tubular system. The film thickness is about 5 to 200 μm, preferably 10 to 200 μm.
About 50 μm is desirable. In addition, the film or sheet of the above-mentioned polyamide-based resin, if necessary, can be coated with an anchor coating agent or the like and subjected to a surface smoothing treatment, etc., and also a corona discharge treatment, a plasma discharge treatment,
A surface treatment such as an ozone treatment, a flame treatment, and others can be arbitrarily performed. In the present invention, by using a polyamide resin (nylon) film or sheet as described above as a substrate, the strength, impact resistance, piercing resistance and other toughness of the film or sheet are utilized to make them available. A laminated material having the following characteristics can be manufactured.
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, a resin film or sheet containing them can also be used.

Next, in the present invention, the heat-sealing resin forming the heat-sealing resin layer constituting the laminate using the barrier film according to the present invention can be melted by heat and fused to each other. Resin films or sheets can be used, and specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer , Ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene Polymer, polyolefin such as polyethylene or polypropylene Resin acrylic acid, methacrylic acid,
Resins such as acid-modified polyolefin resin modified with unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, etc. Film or sheet can be used. Thus, the above-mentioned film or sheet can be used in the form of a coating film of a composition containing the resin. The thickness of the film or film or sheet is 5
μm to 300 μm, more preferably 10 μm to 300 μm.
μm to 100 μm is desirable.

In the present invention, as the heat-sealable resin forming the heat-sealable resin layer, it is particularly preferable to use an ethylene / α-olefin copolymer polymerized using a metallocene catalyst. It is. Thus, as the ethylene / α-olefin copolymer polymerized using the above metallocene catalyst, for example, a catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane with alumoxane, And an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst. Metallocene catalyst, the current catalyst,
The active sites are heterogeneous and are called multi-site catalysts, whereas the active sites are uniform and are also called single-site catalysts. Specifically, the product name "Kernel" manufactured by Mitsubishi Chemical Corporation, the product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd., the product name "EXACT" manufactured by EXXON CHEMlCAL, USA ", A brand name" Affinity "manufactured by Dow Chemical (USA), a brand name" Engage (E
NGAGE) or the like, and an ethylene / α-olefin copolymer polymerized by using a metallocene catalyst.

In the present invention, the resin of the ethylene / α-olefin copolymer polymerized by using the metallocene catalyst as described above may be a film or sheet thereof, or a composition containing the copolymer. It can be used as a coating film, etc.,
It functions as a film or sheet of a resin having heat sealing properties that constitutes the innermost layer. Thus, due to its low temperature heat sealing properties, in post-processing such as bag making, cracks and the like that occur in inorganic oxide thin films and the like. It is possible to prevent occurrence. The thickness of the film or film or sheet is preferably about 3 μm to 300 μm, and more preferably about 5 μm to 100 μm. In the present invention, an ethylene-α-olefin copolymer obtained by polymerization using the above metallocene catalyst,
Further, for example, a partially crosslinked ethylene-propylene rubber (E
PDM), ethylene-propylene rubber (EPR), styrene-butadiene-styrene block copolymer (S
BS), styrene-isobutylene-styrene block copolymer (SIS), styrene-ethylene-butylene-
It is also possible to use a heat-sealable resin layer of a resin composition to which one or more thermoplastic elastomers such as styrene block copolymer (SEBS) are added. In the present invention, as the heat-sealing resin layer, for example, a linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst are used. It may be a multilayer heat-sealable resin layer made of a co-extruded film formed by co-extrusion.

In the present invention, in addition to the above-mentioned heat-sealing resin layer, examples of the laminated material according to the present invention include various resin films, paper base materials, metal materials, synthetic paper, cellophane, and the like. It is possible to manufacture various laminated materials by arbitrarily combining with packaging materials and the like that compose packaging containers such as, etc., and to manufacture a packaging material family suitable for filling and packaging various articles that can be boiled or retorted. It is assumed that. As the film of the above resin, 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 Polymer (AB Resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose And any other known resin film or sheet. In the present invention, the film or sheet is unstretched,
Any material such as one stretched in a uniaxial or biaxial direction can be used. The thickness is arbitrary, but can be selected from a range of several μm to about 300 μm. Further, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film. Further, in the above, as the paper substrate, for example, a paper substrate such as a strongly sized bleached or unbleached paper substrate, or a paper substrate such as pure white roll paper, kraft paper, paperboard, processed paper, or the like may be used. Can be. In the above, as the paper base material constituting the paper layer, it is desirable to use a base material having a basis weight of about 80 to 600 g / m ² , preferably a base weight of about 100 to 450 g / m ² . In the above, as the metal material, for example, aluminum foil, or
A resin film having an aluminum evaporated film or the like can be used.

Next, in the present invention, a method of manufacturing a laminated material using the above-described materials will be described. Examples of the method include a method of laminating a normal packaging material family, for example, wet lamination. Method, dry lamination method, solvent-free dry lamination method, extrusion lamination method, T-die extrusion molding method, co-extrusion lamination method, inflation method, co-extrusion inflation method, and the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a corona treatment, an ozone treatment, a flame treatment, and other pretreatments such as can be applied to the film, and, for example, polyester , Isocyanate (urethane), polyethyleneimine, polybutadiene, organotitanium and other anchor coating agents, or polyurethane, polyacryl, polyester, epoxy, polyvinyl acetate, cellulose, etc. Known anchor coat agents such as laminating adhesives, adhesives and the like can be used.

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using a laminated material manufactured by such a method, facing the surface of the heat-sealing resin layer of the inner layer, and depositing or laminating it, or heat-sealing the peripheral edge thereof Thus, a bag can be formed by providing a seal portion. Thus, as a bag-making method, the above-mentioned composite film is folded with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further sealed, for example, by a side seal type. , Two-sided seal type, three-sided seal type, four-sided seal type, envelope pasted seal type, gassho pasted seal type (pillow seal type),
Various types of packaging containers according to the present invention can be manufactured by heat sealing using a heat sealing mode such as a pleated sealing type, a flat bottom sealing type, a square bottom sealing type, and the like. In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can be manufactured using the above-described composite film. In the above, as a method of heat sealing, for example, a known method such as a bar seal, a rotating roll seal, a belt seal, an impulse seal, a high-frequency seal, and an ultrasonic seal can be used.
In the present invention, in the packaging container as described above, for example, one-piece type, two-piece type,
A spout or the like, or a zipper for opening and closing can be optionally attached.

Next, in the case of a liquid-filled paper container containing a paper base as the packaging container, for example, as a lamination material, a laminate in which paper bases are laminated is manufactured, and a desired paper container is manufactured therefrom. A blank plate is manufactured, and thereafter, a body portion, a bottom portion, a head portion, and the like are manufactured using the blank plate to manufacture, for example, a brick type, a flat type, or a gobel top type liquid paper container. it can. Moreover, the shape can be manufactured using any of a rectangular container, a circular 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, preventing the peeling of the thin film of the inorganic oxide as a barrier film, and preventing the occurrence of thermal cracks, preventing its deterioration, exhibit excellent resistance as a barrier film,
For example, food and drink, pharmaceuticals, detergents, shampoos, oils,
It is excellent in filling and packaging suitability, preservation suitability, etc. of various articles such as chemicals or cosmetics such as toothpaste, adhesives and adhesives, and others. In particular, the laminated material according to the present invention, a packaging bag made by using the same, is filled with the contents from the opening thereof, and then the opening is sealed by heat sealing or the like. After the body is manufactured, the package is placed in, for example, a retort pot and retorted at 120 ° C. for 30 minutes to produce a retorted (sterilized) packaged product. Further, using the laminated material according to the present invention, the contents are filled and packaged in the same manner as described above in a packaging bag formed by bag making, and a package is manufactured. For 30 minutes to produce a package product heat-sterilized.

FIG. 4 shows another example of a plasma chemical film forming apparatus 11 for producing a barrier film.
Also in this example, the substrate 1 is wound around the unwinding roll 31 disposed in the vacuum chamber 12. The base material 1 pulled out from the unwinding roll 31 includes auxiliary rolls 32, 3
3, the film is wound around a film forming drum 34, and is further wound around a winding roll 35 via guide rolls 32 'and 33'. In this example, the infrared lamp 36 as a heating means is connected to the in-line guide rolls 32 and 3 so as to heat the back surface 1b of the substrate 1 (the surface in close contact with the film forming drum 34).
It is arranged only on the upper side between the three. Then, the back surface 1b of the substrate 1 is irradiated with heat rays to remove moisture contained in the substrate 1 by a pretreatment for film formation. The width of irradiating the substrate 1 with the infrared lamp 36 is from 100% to the width of the entire substrate 1.
The irradiation length L is set to about 20 to 50 cm when the traveling speed of the base material is about 100 m / s. Further, the irradiation time of the infrared lamp 36 is set to a time sufficient for moisture in the base material 1 to evaporate and exit from the inside to the outside, and the temperature of the heated base material 1 damages the base material 1 itself. Is set so as not to give the glass transition temperature. The moisture content of the moisture in the substrate 1 by the infrared lamp 36 is 0.3 in the case of a polyamide resin film.
% To 0.5%).

As described above, the water is removed by heating the back surface 1b of the substrate 1 in the pretreatment before the film formation. Therefore, the quality of film formation and the like is maintained high without moisture evaporating from the substrate 1 during film formation.

FIG. 5 shows still another example of the plasma chemical film forming apparatus 11. In this example, the infrared lamp 3
Instead of 6, a heat roller 37 is used as a heating element. Other configurations are the same as those of the example using the infrared lamp 36, and thus the same reference numerals are given and the description is omitted. The heat roller 37 is disposed between the in-line guide rolls 32 and 33, and is in contact with the back surface 1b of the substrate 1 on which the heat roller 37 runs. Then, heat is conducted from the heated hot roller 37 on the high temperature side to the base material 1 on the low temperature side. The temperature of the heat roller 37 is set to be equal to or lower than the glass transition temperature of the substrate 1, for example, about 60 ° C. so as not to damage the substrate 1. Is set to about 2 m when is about 100 m / s). The contact time between the heat roller 37 and the substrate 1 is set to a time sufficient for moisture in the substrate 1 to evaporate and go from the inside to the outside. The heat roller device 37 reduces the moisture content of the moisture in the base material 1 to, for example, about 0.5 to 1.0% in the case of a polyamide resin film.

FIG. 6 shows still another example of the plasma chemical film forming apparatus 11. In this example, a microwave heating device 38 is used as a heating unit. Other configurations are the same as those of the example using the infrared lamp 36, and thus the same reference numerals are given and the description is omitted. The microwave heating device 38 is provided with an in-line guide roll 3.
2 and 33, which apply a high-frequency electromagnetic field to the substrate 1 to heat the back surface 1b of the substrate 1. The temperature of the base material 1 heated by the microwave heating device 38 is set to a glass transition temperature or lower so as not to damage the base material 1 itself, and the heating time is determined by evaporating moisture in the base material 1 and Is set to a time sufficient to go outside. By the microwave heating device 38, the moisture content of the moisture in the base material 1 is reduced to about 0.5% to 1.0% in the case of a polyamide resin film.

As the heating device, in addition to the above, various heating devices such as an electron beam (EB) heating device for irradiating the substrate 1 with an electron beam, a resistance heating device, and a high-frequency heating device can be used.

In the pretreatment, besides heating the substrate 1, the back surface 1b of the substrate 1 may be modified by a surface activation treatment such as a plasma treatment or a corona treatment. For example, the plasma CVD apparatus 11 may be provided with a plasma generation port (not shown) for performing plasma processing on the back surface 1b of the base material 1 before forming the barrier layer 2 in-line. The plasma generating port generates a gas plasma such as argon acid toward the back surface 1b of the substrate 1. A DC glow discharge device, a high-frequency discharge device, a microwave discharge device, and the like (not shown) are provided to generate gas plasma from the plasma generation port.

By this plasma treatment, the adsorbed water on the back surface 1b of the substrate 1 is beaten out in a liquid state, the surface layer of the back surface 1b is melted and densified, and the moisture in the substrate 1 does not go outside. In addition, by the plasma treatment, the moisture content in the base material 1 is 1.5% before the treatment in the case of the polyamide resin film.
２2% to about 0.2 to 1.0%. In the case where a silicon oxide barrier layer is formed by a plasma chemical film forming method as described above in a later film forming step, the moisture content of the substrate is set to 0.3%.
It is preferable to adjust the thickness to about 0.5% to form a film. The water content is adjusted by the plasma output of the plasma processing, the type of gas, the gas supply amount, the processing time, and the like. The moisture content can be measured by the Karl Fischer method or the like, and the degree of modification can be known by measuring the smoothness of the back surface 1b with a surface roughness measuring device or the like.

In this embodiment, the modification is performed in-line during the film formation in the plasma processing apparatus 11, but may be performed off-line before the base material 1 is incorporated into the plasma chemical film formation apparatus 11. Good. For the modification of the back surface 1b, a surface activation treatment such as a corona treatment, a flame treatment, or a glow discharge plasma treatment using a vacuum other than the plus treatment can be used.

As the substrate 1 used in the plasma chemical film forming apparatus 11, not only a polyamide resin but also various resin films such as a polypropylene resin film containing water and a polyethylene terephthalate resin film can be used. Can be. Specifically, polyester, nylon, polyethylene, polypropylene, polyvinyl chloride,
Examples include stretched or unstretched resin films such as polycarbonate, polyvinyl alcohol, cellulose, polyacrylate, polyurethane, cellophane, polyethylene terephthalate, and ionomer. The thickness of the substrate 1 can be appropriately set based on the purpose of use of the barrier film and the stability at the time of production.
It can be about μm.

[0052]

Next, the present invention will be described in more detail with reference to examples of the present invention. Example (1). As a base material, a biaxially stretched nylon 6 film having a thickness of 15 μm (manufactured by Toyobo Co., Ltd., N-110
2) is mounted on a delivery roll of a plasma chemical film forming apparatus, and then, when the biaxially stretched nylon 6 film is fed to a film forming drum, the biaxially stretched nylon 6 film is biaxially stretched using a 500 W infrared lamp. Both surfaces of the nylon 6 film are irradiated with heat rays from the above-mentioned infrared lamp to remove water contained in the above-mentioned biaxially stretched nylon 6 film according to the thin film forming speed shown below. A thin film of silicon oxide having a thickness of 140 ° was formed on one surface of the film under the following plasma chemical film formation conditions to produce a barrier film according to the present invention. (Plasma chemical vapor deposition conditions) Reaction gas mixed group: hexamethyldisiloxane: oxygen gas: helium = 3: 1: 3 (unit: slm, standard liter minit, standard lit)
er minute, the same shall apply hereinafter) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 6.0 × 10 ⁻³ mbar Cooling / electrode drum supply power: 10 kW Thin film formation speed: 100 m / In the above, as a result of irradiating heat rays from an infrared lamp, the moisture content in the biaxially stretched nylon 6 film was reduced from the initial moisture content of 3% to 0.3% after irradiation and film formation. . (2). Next, the surface of the silicon oxide thin film of the barrier film produced above was subjected to plasma treatment under the following conditions. As a result, the surface tension of the silicon oxide thin film surface becomes 35 dyn
To 62 dyn, and the wettability was improved. Plasma supply power: 3 kW Plasma gas: Mixed gas of helium (He) and oxygen (O ₂ ) (3). Next, using the above-mentioned plasma-treated barrier film, this was attached to one of the delivery rolls of a dry laminating coater machine, an adhesive layer was formed on the thin film surface of silicon oxide, and the other thickness was a sealant film. 4
A 0 μm unstretched polypropylene film was used and mounted on the other delivery roll, and then both were dry-laminated under the following conditions to produce a laminated material. Adhesive layer: Use urethane-based adhesive (Main agent) Urethane-based (manufactured by Takeda Pharmaceutical Co., Ltd., trade name, Takenate A-515) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd., trade name, A- 50) (Mixing ratio) Main agent: Curing agent = 10: 1 (Solvent) Ethyl acetate (Coating amount) 4.0 g / m ² (Dry)

Comparative Example 1 (1). As a base material, a biaxially stretched nylon 6 film having a thickness of 15 μm (manufactured by Toyobo Co., Ltd., N-110
2) is mounted on a delivery roll of a plasma chemical film forming apparatus, and a 140 ° -thick silicon oxide thin film is formed on the surface of the biaxially stretched nylon 6 film under the following plasma chemical film forming conditions. Thus, a barrier film was manufactured. (Plasma chemical vapor deposition conditions) Reaction gas mixture ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 3: 1: 3 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Inside vapor deposition chamber Vacuum degree: 6.0 × 10 ⁻³ mbar Cooling / electrode drum supply power: 10 kW Thin film formation speed: 100 m / min In the above description, the moisture content in the biaxially stretched nylon 6 film is the moisture content before film formation. It was 3%, and the moisture content after film formation was 2.5%. (2). Next, the surface of the silicon oxide thin film of the barrier film produced above was subjected to plasma treatment under the following conditions. As a result, the surface tension of the silicon oxide film was 35 dyn.
To 62 dyn, and the wettability was improved. Plasma supply power: 3 kW Plasma gas: Mixed gas of helium (He) and oxygen (O ₂ ) (3). Next, using the plasma-treated barrier film described above, this is mounted on one of the delivery rolls of a dry laminating coater machine, an adhesive layer is formed on the silicon oxide thin film surface, and the other is a sealant film. A non-stretched polypropylene film having a thickness of 40 μm was used, mounted on the other delivery roll, and then both were dry-laminated under the following conditions to produce a laminated material. Adhesive layer: Use urethane-based adhesive (Main agent) Urethane-based (manufactured by Takeda Pharmaceutical Co., Ltd., trade name, Takenate A-515) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd., trade name, A- 50) (Mixing ratio) Main agent: Curing agent = 10: 1 (Solvent) Ethyl acetate (Coating amount) 4.0 g / m ² (Dry)

Comparative Example 2 (1). A roll-up type vacuum evaporation apparatus is used, and a 15 μm-thick biaxially stretched nylon 6 film (manufactured by Toyobo Co., Ltd., N-1102) is used as a base material. Was used as a vapor deposition source to form a 140 ° -thick silicon oxide vapor-deposited film by a vacuum vapor deposition method using an electron beam (EB) heating method, thereby producing a barrier film. (2). Next, the surface of the thin film of silicon oxide deposited on the barrier film produced above was subjected to plasma treatment under the following conditions. As a result, the surface tension of the silicon oxide deposited thin film surface is
Plasma supply power: 3 kW Plasma gas: a mixed gas of helium (He) and oxygen (O ₂ ), from 35 dyn to 62 dyn and improved wettability (3). Next, using the plasma-treated barrier film above, it was mounted on one of the delivery rolls of a dry laminating coater machine, an adhesive layer was formed on the silicon oxide vapor-deposited thin film surface, and the other was a sealant film. A non-stretched polypropylene film having a thickness of 40 μm was used, and this was mounted on the other delivery roll, and then both were dry-laminated under the following conditions to produce a laminated material. Adhesive layer: Use urethane-based adhesive (Main agent) Urethane-based (manufactured by Takeda Pharmaceutical Co., Ltd., trade name, Takenate A-515) (Curing agent) Isocyanate-based (Takeda Pharmaceutical Co., Ltd., trade name, A- 50) (Mixing ratio) Main agent: Curing agent = 10: 1 (Solvent) Ethyl acetate (Coating amount) 4.0 g / m ² (Dry)

Experimental Example 1 Each of the barrier films produced in Example 1 and Comparative Examples 1 and 2, and. The following data was measured about the laminated material. (1). Oxygen permeability measurement This is the barrier film and, for the laminate,
The measurement was carried out under the conditions of a temperature of 23 ° C. and a humidity of 90% RH with a measuring device (model name, OXTRAN) manufactured by MOCON, USA. (2). Measurement of water vapor permeability This is a barrier film and, for a laminate,
The measurement was carried out under the conditions of a temperature of 40 ° C. and a humidity of 90% RH with a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA. (3). Boil aptitude evaluation This uses a laminated material, the unstretched polypropylene film surfaces are opposed to each other, and the outer peripheral edge is heat-sealed to produce a packaging bag. After that, the opening is sealed to produce a package, and the package is immersed in boiled water at 90 ° C. for 30 minutes for boil treatment. The permeability and the water vapor permeability were measured and evaluated. (4). Retort suitability evaluation In the same manner as above, using a laminated material, the unstretched polypropylene film surfaces are opposed to each other, and the outer peripheral end is heat-sealed to produce a packaging bag. After filling the contents and then closing the opening, a package is manufactured. The package is placed in a retort pot and retorted at 120 ° C. for 30 minutes. The permeability and the water vapor permeability were measured and evaluated. The above measurement results are shown in Tables 1, 2 and 3 below.

[0056]

[Table 1] 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. (After lamination) indicates the oxygen permeability and the water vapor permeability of the laminated material.

[0057]

[Table 2] In Table 2 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.

[0058]

[Table 3] In Table 3 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.

(1). As is clear from the results shown in the above Tables 1 to 3, the oxygen permeability and the water vapor permeability of Example 1 are those of Comparative Examples 1 to 2 before boiling and before retorting. It was excellent compared to. (2). Further, in the case of Example 1, the oxygen permeability and the water vapor permeability were all far superior to those of Comparative Examples 1 and 2 even after boiling and after retorting. .

[0060]

As is apparent from the above description, the present invention irradiates a polyamide-based resin film with heat rays to remove moisture, and has a relatively high flexibility and a high followability, and is free from cracks and the like. Focusing on the thin film by the plasma chemical film formation method, which can suppress the generation and has almost no deterioration in the barrier property, first irradiate the polyamide resin film with heat rays from the infrared lamp in advance using an infrared lamp or the like. Then, moisture contained in the polyamide-based resin film is removed, and then a thin film of an inorganic oxide such as silicon oxide is provided on one surface of the polyamide-based resin film by a plasma chemical film-forming method. To produce a functional film,
On the thin film surface of the inorganic oxide of the barrier film, at least, to provide a heat-sealing resin layer and the like to produce a laminated material,
Next, using the laminated material, a bag is produced from the laminated material to produce a packaging container. Thereafter, the contents are filled and packaged in the packaging container, and the opening is heat-sealed to form a package. When a thin film of an inorganic oxide such as silicon oxide was formed, almost no phenomenon that water and the like emerged from the polyamide-based resin film was observed, and the surface of the polyamide-based resin film was not affected. In addition, a thin film of an inorganic oxide such as silicon oxide can be formed extremely well, and the adhesion between the polyamide resin film and a thin film of an inorganic oxide such as silicon oxide is excellent. It has an extremely high barrier property against gas or water vapor, etc., and has excellent transparency, and also has excellent laminate strength and the like.
A barrier film useful for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, and the like, and a laminated material using the same can be produced.

[Brief description of the drawings]

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

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

FIG. 3 is a schematic configuration diagram of a plasma chemical film forming apparatus illustrating an example of a method for producing a barrier film according to the present invention.

FIG. 4 is a schematic configuration diagram showing another example of the plasma chemical film forming apparatus.

FIG. 5 is a schematic configuration diagram showing still another example of the plasma chemical film forming apparatus.

FIG. 6 is a schematic configuration diagram showing still another example of the plasma chemical film forming apparatus.

[Explanation of symbols]

 Reference Signs List A barrier film B laminated material 1 polyamide-based resin film (base material) 2 inorganic oxide thin film 3 heat-sealing resin layer 11 plasma chemical film formation device 12 vacuum chamber 13,31 unwind roll 14,32 guide roll 14 ' , 32 'guide roll 15, 33 guide roll 15', 33 'guide roll 16, 34 film forming drum (film forming means) 17, 18 infrared lamp 19, 20, 21 raw material volatile supply device 22 raw material supply nozzle 23 glow Discharge plasma 24 Power supply 25 Magnet 26, 35 Take-up roll 27 Vacuum pump 36 Infrared lamp (pre-processing means, heating device) 37 Heat roller (pre-processing means, heating device) 38 High-frequency heating device (pre-processing means, heating device)

Continued on the front page (72) Inventor, Hisashi Sakamoto 1-1-1, Ichigaga-cho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd. F-term (reference) 3E086 AD01 BA02 BA04 BA15 BA33 BA40 BB02 BB05 BB22 CA01 CA28 CA29 CA35 DA01 4F006 AA38 AB76 BA05 CA07 DA01 EA02 EA05 4F100 AA01B AA20B AK46A AK48A AR00C BA02 BA03 BA07 BA10B BA10C EJ38A EJ421 EJ43A EJ461 EJ531 EJ551 EJ61B EJ612 EJ682 EJ86A EJ861 EK08 GB15 GB23 JA20B JD01 JD03 JD04 JD15 JJ03 JL12C YY00 YY00B 4K030 AA06 AA09 AA14 BA42 BA44 CA07 CA12 DA03 DA08 FA01 FA03 GA14 JA01 LA01 LA24

Claims (26)

[Claims] 1. A barrier film characterized in that a thin film of an inorganic oxide is provided on one surface of a polyamide-based resin film from which moisture contained therein has been removed by irradiation with heat rays by a plasma chemical film formation method. 2. The barrier film according to claim 1, wherein the heat ray comprises a heat ray irradiated by using an infrared lamp. 3. The polyamide resin film according to claim 1, wherein the polyamide resin film is a polyamide resin film from which water contained therein has been removed by irradiating heat rays in-line to form a thin film of an inorganic oxide by a plasma chemical film forming method. 1 or 2
4. The barrier film according to 1. 4. The barrier film according to claim 1, wherein the polyamide resin film comprises a biaxially stretched nylon film. 5. The barrier film according to claim 1, wherein the inorganic oxide thin film comprises a silicon oxide thin film formed by a plasma chemical film forming method. 6. The inorganic oxide thin film has a thickness of 50 to 50.
The barrier film according to any one of claims 1 to 5, wherein the angle is 0 °. 7. A thin film of an inorganic oxide having a thickness of 100.degree.
The barrier film according to any one of claims 1 to 6, wherein the angle is 50 °. 8. The barrier film according to claim 1, wherein the moisture content of the polyamide resin film after forming the inorganic oxide thin film is 1.5% or less. 9. An inorganic oxide of a barrier film having a structure in which a thin film of an inorganic oxide is provided on one surface of a polyamide resin film from which moisture contained therein has been removed by irradiation with heat rays by a plasma chemical film formation method. At least on the thin film surface of
A laminated material comprising a heat-sealing resin layer. 10. A method for producing a barrier film, comprising: performing a pretreatment on the back surface of a film-like substrate to suppress the release of moisture, and forming a barrier layer on the surface of the substrate. 11. A method for producing a barrier film, wherein a barrier layer is formed on a surface of a running substrate by a plasma-enhanced chemical film deposition method while continuously moving the film-shaped substrate. A method for producing a barrier film, comprising performing a pretreatment for removing moisture from the substrate before forming a layer. 12. The method according to claim 10, wherein in the pretreatment, the base material is heated. 13. The method for producing a barrier film according to claim 10, wherein in the pretreatment, a back surface of the base material is heated. 14. The substrate according to claim 12, wherein the substrate is heated by irradiating the substrate with heat rays.
4. The method for producing a barrier film according to item 3. 15. The method for producing a barrier film according to claim 12, wherein a heating element is brought into contact with the running base material to heat the base material. 16. The substrate according to claim 12, wherein a high-frequency electromagnetic field is applied to the moving substrate to heat the substrate.
Or a method for producing a barrier film according to item 13. 17. The method according to claim 12, wherein the substrate is heated by irradiating the traveling substrate with an electron beam. 18. The method according to claim 10, wherein the back surface of the base material is modified in the pretreatment. 19. The method according to claim 18, wherein the base material is modified by plasma treatment or corona treatment. 20. A method according to claim 1, further comprising: a pretreatment unit for performing a pretreatment for suppressing release of moisture from the back surface of the film-like base material; For manufacturing a barrier film. 21. An apparatus for producing a barrier film, wherein a barrier layer is formed on a surface of a running substrate by a plasma chemical film formation method while continuously running the film-shaped substrate. An apparatus for producing a barrier film, comprising a pretreatment means for removing water from the substrate before forming a layer. 22. The barrier film manufacturing apparatus according to claim 20, wherein the pretreatment means has a heating device for heating the base material. 23. The barrier film manufacturing apparatus according to claim 20, wherein the pretreatment unit modifies the back surface of the base material by plasma treatment or corona treatment. 24. A barrier film, wherein a barrier layer is formed on the surface of a film-like base material whose back surface has been subjected to a pretreatment for suppressing release of moisture. 25. A barrier film having a barrier layer formed on one surface of a film-like substrate from which water contained has been removed by heating by a plasma chemical film formation method. 26. A barrier film, wherein a barrier layer is formed on the surface of a film-like base material having a modified back surface by a plasma chemical film formation method.