JP2001277419A - Transparent barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent barrier film having a polyamide resin film as a base material, excellent in transparency and barrier properties of oxygen, steam or the like, preventing the generation of a crack caused by bending or stretching, made excellent in post-processability to suppress the lowering of the barrier properties, increased in production line speed to be enhanced in production efficiency and useful for packaging various articles, especially after boiling or retorting treatment, and a laminated material using the same. SOLUTION: A plasma treatment surface is provided on one surface of a polyamide resin film and a vapor deposition film of an inorganic oxide with a thickness of 4-10 nm due to a chemical vapor phase growing method is provided on the plasma treatment surface to constitute a transparent barrier film. A water-resistant film may be preliminarily provided on the other surface of the polyamide resin film.

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 laminated material using the same, and more particularly, to a film having excellent transparency, a barrier property for preventing permeation of oxygen and water vapor, etc. Prevents the occurrence of cracks due to expansion and contraction, then suppresses the reduction in barrier properties due to excellent workability, and also increases the production line speed to improve the production efficiency.Filling and packaging of various articles, especially, The present invention relates to a transparent barrier film useful for filling and packaging by boil treatment or retort treatment and a laminated material using the same.

[0002]

2. Description of the Related Art Various types of packaging materials using a polyamide resin film as a base film and having a barrier property for preventing permeation of oxygen, water vapor and the like have been developed and proposed. The most common is a barrier packaging material in which a barrier layer made of, for example, a polyvinylidene chloride resin or a polyvinyl chloride resin is provided on one surface of a polyamide resin film. Further, as a barrier packaging material using a polyamide resin film as a base film, a co-extruded multilayer nylon film having nylon MXD-6 having a high barrier property as an intermediate layer is also known. Thus, in recent years, as a barrier packaging material having high barrier properties and exhibiting a stable fragrance retention property and further having a high transparency, for example, a physical vapor phase is applied to one surface of a polyamide resin film. A transparent barrier film having a configuration in which a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided by a growth method or a chemical vapor deposition method has been developed and proposed. The barrier packaging material as described above is arbitrarily laminated with a material such as another plastic film, a paper base, or the like to produce a desired packaging laminate, and then used to make a bag. It is manufactured in a box to produce packaging containers of various forms, and thereafter, is used widely for filling and packaging various articles such as foods and drinks.

[0003]

However, for example, the above-mentioned polyamide resin film is provided on one side with a barrier layer made of, for example, a polyvinylidene chloride resin or a polyvinyl chloride resin. Since the materials for use contain chlorine atoms, there is a problem that if incineration is performed after use, chlorine gas is generated, which is not preferable for environmental hygiene. Moreover, in the co-extruded multilayer nylon film having the above-described nylon MXD-6 having a high barrier property as an intermediate layer, the barrier performance as a barrier packaging material is inferior, and it cannot be said that it is still sufficiently satisfactory. In particular, there is a problem that the barrier properties are significantly affected by temperature, humidity, and the like. Further, on one side of the polyamide-based resin film, silicon oxide by a physical vapor deposition method or a chemical vapor deposition method, a transparent barrier film having a configuration in which an inorganic oxide deposited film such as aluminum oxide is provided, Compared to conventional aluminum foil and other barrier packaging materials, it has excellent transparency and high barrier properties against oxygen, water vapor, etc., and also has excellent fragrance retention for contents, etc. There is no environmental problem at the time of disposal, and the demand for packaging materials is greatly expected.

However, in the laminated material using the above-mentioned transparent barrier film, the deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is glassy and is inferior in flexibility. When the laminated material is rounded or bent, cracks and the like are easily generated in the deposited film of the inorganic oxide. Thus, once cracks or the like occur in the deposited film, there is a problem that the barrier property is significantly reduced. Further, in the above-mentioned transparent barrier film, for example, in order to improve the barrier properties, it is often attempted to increase the thickness of the inorganic oxide deposited film, in this case, the inorganic oxide Increasing the thickness of the vapor-deposited film, on the other hand, tends to cause cracks and the like, and has the same problems as described above. Further, on one side of the polyamide resin film, a transparent barrier film having a configuration in which a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided by a physical vapor deposition method, Of polyamide resin film,
Compared to a polyester resin film generally used as a base material for vapor deposition, it swells due to the absorption of moisture and water vapor, and its dimensional change is as large as about 2 to 10 times. At the time of the formation of the deposited film of the product, it is extremely difficult for the deposited film of the inorganic oxide to follow the dimensional change of the polyamide resin film,
When a vapor-deposited inorganic oxide film is formed by physical vapor deposition, it is practically impossible to use a polyamide resin film as a base film for vapor deposition. is there. Further, in order to obtain a sufficient barrier performance in a transparent barrier film having a structure in which a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of the above-mentioned polyamide resin film by chemical vapor deposition. Requires that the thickness of the deposited film of the inorganic oxide such as silicon oxide or aluminum oxide formed by chemical vapor deposition be reduced to at least a thickness exceeding 10 nm. In order to form an inorganic oxide vapor-deposited film having such a thickness, there is a problem that the line speed at the time of film formation cannot be increased, and the production efficiency is significantly reduced.

[0005] Further, the above-mentioned barrier packaging material having a polyamide resin film as a base film may be arbitrarily laminated with other plastic films, paper substrates, and other materials to form a desired packaging laminate. Producing materials, and then using them to make bags or boxes to produce packaging containers of various forms, and then using them to produce various articles such as food and drink Filling and packaging, and then, for the purpose of sterilization or sterilization of the contents, such as boil treatment or retort treatment, as described above, the polyamide resin film swells due to the absorption of moisture, steam, etc. Since the change is as large as about 2 to 10 times, it is actually difficult to produce a sufficiently satisfactory packaged product even by the boil treatment or the retort treatment. Therefore, the present invention uses a polyamide-based resin film as a base film for vapor deposition, and has excellent transparency, a barrier property for preventing permeation of oxygen, water vapor, and the like, and further prevents cracks caused by bending and expansion and contraction. After that, it is excellent in processability and suppresses the deterioration of barrier property, and also increases the production line speed to improve the production efficiency, and fills and packs various articles, particularly, performs boil processing or retort processing and fills and packs. It is an object of the present invention to provide a transparent barrier film useful for the above and a laminated material using the same.

[0006]

As a result of various studies to solve the above problems, the present inventor has used a polyamide resin film as a base film for vapor deposition, and On one surface of the system resin film, a plasma treatment surface is provided, and further, on the surface of the plasma treatment surface, a vapor-deposited film of an inorganic oxide such as silicon oxide by a chemical vapor deposition method,
A transparent barrier film is manufactured by forming a film having a thickness in the range of 4 nm to 10 nm, or a water-resistant film is provided in advance on one surface of the polyamide resin film, and plasma treatment is first performed on the other surface. A surface is further provided, and a vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the surface of the plasma-treated surface by a chemical vapor deposition method in a thickness of 4 nm to 10 nm to produce a transparent barrier film. Then, for example, a heat-sealing resin layer, a base film layer and the like are laminated on the transparent barrier film produced above to produce a packaging laminate, and the packaging laminate is further used. Then, the container for packaging is manufactured by bag making or box making, and thereafter, the container for packaging is used, and this is filled and packed with various articles, and further, if necessary, treated by boiling or retorting. After manufacturing packaging products, Excellent adhesion between the amide-based resin film and the deposited film of inorganic oxide such as silicon oxide, and excellent transparency, barrier properties to prevent transmission of oxygen and water vapor, etc. Prevents the occurrence of cracks, then suppresses the decline in barrier properties due to excellent workability, and also increases the production line speed to improve its production efficiency, and also improves the water resistance of the polyamide resin film, The present invention has been completed by finding that a transparent barrier film useful for filling and packaging of articles, particularly a boil or retort treatment and filling and packaging, and a laminated material using the same can be produced.

That is, according to the present invention, a plasma-treated surface is provided on one surface of a polyamide resin film, and a film thickness of 4 n
A transparent barrier film characterized by having an inorganic oxide deposited film of m to 10 nm, or a polyamide resin film, on one surface, a water-resistant film is provided in advance, and on the other surface, , A plasma-treated surface, and a 4n-thick film formed by chemical vapor deposition on the surface of the plasma-treated surface.
The present invention relates to a transparent barrier film provided with an inorganic oxide vapor-deposited film having a thickness of 10 to 10 nm, and a laminated material using the transparent barrier film.

Incidentally, a transparent barrier film having a structure in which an inorganic oxide deposited film such as silicon oxide or aluminum oxide is provided on one side of the above-mentioned polyamide resin film by physical vapor deposition or chemical vapor deposition. In practice, for example, small bags for liquids for filling and packaging soy sauce, soups, soups, etc., soft packaging bags for filling and packaging raw confectionery, etc., or soft packaging for filling and packaging boiling or retort foods, etc. It is used as a barrier packaging material constituting a packaging bag or the like. Thus, for example, the above-mentioned soy sauce, soy sauce
In the case of a transparent barrier film used as a barrier packaging material constituting a liquid pouch for filling and packaging a soup or soup, or a soft packaging bag for filling and packaging a boil or retort food, etc. Since most of the contents filled and packed in the packaging bag are water, it is not so important to prevent the invasion of moisture and the like from the outside air. Also, in the case of a transparent barrier film used as a barrier packaging material constituting a soft packaging bag for filling and packaging the above-mentioned raw confectionery, etc., it is difficult for moisture contained in the raw confectionery or the like to escape from the inside to the outside. However, there is a problem that dew condensation due to moisture or the like occurs on the inner wall, and the contents and the like cannot be visually recognized.

Therefore, the above-mentioned transparent barrier film has
Mainly, when used as a packaging material for barrier properties in the above-mentioned applications, the water vapor barrier property for preventing the permeation of water vapor is not so important physical property, and the heat-sealing material constituting the sealant layer is not so important. -It is possible to sufficiently cope with the water vapor barrier property of a polyolefin resin film as a rollable resin. For this reason, conventionally, a vapor-deposited film of an inorganic oxide having a film thickness of more than 10 nm is formed on one surface of a polyamide-based resin film by a chemical vapor deposition method. First, a plasma-treated surface is provided on one side of the resin film.
It has been found that, within the range of 10 nm to 10 nm, a vapor-deposited film of an inorganic oxide such as silicon oxide is formed into a film, thereby increasing the production line speed of film formation and improving the production efficiency. In addition, while improving the tight adhesion between the polyamide-based resin film and the inorganic oxide vapor-deposited film, the film quality of the inorganic oxide vapor-deposited film is made flexible, and the occurrence of cracks due to bending and expansion and contraction is prevented. By reducing the film thickness, the oxygen gas barrier property for preventing oxygen gas permeation or the water vapor barrier property for preventing water vapor permeation slightly decreases, but the post-processing steps such as printing and laminating are correspondingly reduced. In the above, the barrier property of the deposited film of inorganic oxide due to cracks or the like is suppressed. Furthermore, by providing a water-resistant film on one surface of the polyamide-based resin film in advance, the swelling and dimensional change of the polyamide-based resin film due to the absorption of moisture and water vapor can be prevented. It is possible to form a deposited film of an inorganic oxide such as silicon oxide by satisfactorily and to withstand boil treatment or retort treatment sufficiently, and is excellent in market distribution, storage property, storage stability and the like. A satisfactory packaged product can be produced.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail. First, the configuration of the transparent barrier film according to the present invention and the laminated material and the like using the same will be described with reference to the drawings and the like with specific examples. FIGS. 1 and 2 show the transparent barrier film according to the present invention. FIG. 3 is a schematic cross-sectional view showing a layer configuration of one example of a film, and FIGS. 3 and 4 show examples of a layered material manufactured using the transparent barrier film according to the present invention. It is a schematic sectional drawing which shows a layer structure.

First, as shown in FIG. 1, a transparent barrier film A according to the present invention is provided with a plasma treatment surface 2 on one surface of a polyamide resin film 1, and further, a surface of the plasma treatment surface 2. 4n film thickness by chemical vapor deposition
The basic structure is that it has a configuration in which a deposited film 3 of an inorganic oxide of m to 10 nm is provided. Furthermore, as shown in FIG. 2, the transparent barrier film A _{1 according} to the present invention is formed on one surface of the polyamide resin film 1 in advance.
First, a plasma-treated surface 2 is provided on the other surface, and an inorganic oxide having a thickness of 4 nm to 10 nm is deposited on the surface of the plasma-treated surface 2 by chemical vapor deposition. The basic structure is that it has a configuration in which the film 3 is provided. The above-mentioned examples illustrate one or two examples of the transparent barrier film according to the present invention, and the present invention is not limited thereto. For example, although not shown, in the present invention, the inorganic oxide vapor-deposited film is not only a single layer film composed of one layer of the inorganic oxide vapor-deposited film but also a multilayer film composed of two or more inorganic oxide vapor-deposited films. And the like.

Next, the present invention relates to the above-mentioned present invention.
For laminated materials manufactured using transparent barrier films
This will be explained by exemplifying one or two examples.
As shown in FIG. 3, the laminated material shown in FIG.
In the example using the transparent barrier film A,
Inorganic oxide of the transparent barrier film A shown in FIG.
A primer agent layer 5 and a laminate
At least a heat-sealing tree through the adhesive layer 6 for use.
It is possible to exemplify a laminated material B having a configuration in which the oil layer 7 is provided.
it can. In the present invention, as shown in FIG.
Example using the transparent barrier film A shown in FIG. 1 above
For example, the transparent barrier film shown in FIG.
A primer agent layer 4 and the surface of the inorganic oxide deposited film 3
And at least the heat via the anchor coating agent layer 8.
Laminated material B having a structure provided with a sealing resin layer 7 ₁The example
Can be shown. In the present invention,
No, but of course, the transparent barrier film shown in FIG.
A₁Using the same method as described above,
The laminated material can be manufactured. Also book
In the invention, although not shown, the laminated material according to the present invention
In, the transparent barrier film constituting the laminated material
Add a new surface to the polyamide resin film or water-resistant film.
To the base film layer, or base film layer and
A laminated material having a configuration in which heat-sealing resin layers are laminated is used.
Can be manufactured. Thus, the example given above is
It is an illustration of 12 examples that constitute the laminated material according to the present invention,
The invention is not limited thereby, for example,
In the present invention, although not shown, the base film layer,
-In addition to the sealing resin layer, etc.
Depending on the application, other base materials can be arbitrarily laminated and various forms
Can be designed and manufactured.

Next, in the present invention, an example of the configuration of a packaging container formed by bag making or box making using the above-described laminated material will be described. For example, a description will be given by exemplifying a packaging container made from a bag or a box using the laminated material B shown in FIG. 1. As shown in the schematic perspective view of FIG. Are prepared, and the heatsink located at the innermost layer is prepared.
The surfaces of the conductive resin layers 7 and 7 are superimposed on each other, and thereafter, three sides of the outer peripheral edge are heat sealed to seal.
Are formed, and an opening 10 is formed thereabove.
The three-way seal type flexible packaging container C can be manufactured. Thus, in the present invention, although not shown, from the opening of the three-way seal type soft packaging container manufactured above, for example, the contents such as food and drink, and the like are filled,
Next, the upper opening is heat-sealed to form an upper seal portion and the like, and further subjected to, for example, a boil treatment, a retort treatment, or the like, if necessary, to form packaging in various forms. Products can be manufactured. In the present invention, it is needless to say that the present invention is not limited to the exemplary packaging container illustrated above, and the purpose, use, etc., may be a soft packaging bag, a liquid paper container, a paper can, It goes without saying that various other forms of packaging containers can be manufactured.

Next, in the present invention, the materials constituting the transparent barrier film, the laminated material, etc. according to the present invention as described above, the production method, and the like will be described. First, in the present invention, the transparent barrier according to the present invention is described. As the polyamide-based resin film constituting the conductive film, the laminated material, etc., any polyamide-based resin film capable of holding a non-crystalline thin film of aluminum oxide can be used, for example, nylon 46, Nylon 6, nylon 6
6, nylon 610, nylon 612, nylon 11,
Various polyamide resin films or sheets such as nylon 12 and the like can be used. These polyamide-based resin films or sheets may be uniaxially or biaxially stretched, and have a thickness of about 10 to 200 μm, preferably about 10 to 200 μm.
About 100 μm is desirable. If necessary, the surface of the polyamide resin film or sheet may be subjected to a surface smoothing treatment by coating an anchor coating agent or the like on the surface.

Next, in the present invention, the plasma treated surface constituting the transparent barrier film, the laminated material and the like according to the present invention will be described. The plasma treated surface is obtained by ionizing gas by arc discharge. The plasma-treated surface can be formed by using a plasma surface treatment method for performing surface modification using generated plasma gas. That is, in the present invention, the plasma treatment is performed by a method using one or more kinds of active or inert gases such as oxygen gas, nitrogen gas, argon gas, and helium gas as the plasma gas. A surface can be formed. Thus, in the present invention, the plasma treatment performed on the surface of the polyamide-based resin film includes, during the plasma discharge treatment, an oxygen gas, or a mixed gas of an oxygen gas and an argon gas or a helium gas, or an inert gas. It is preferable to perform the plasma treatment using a gas, and it is possible to perform the plasma treatment at a lower voltage by such a plasma treatment, thereby preventing discoloration or the like of the surface of the polyamide resin film or the like. Thus, a plasma-treated surface can be favorably provided on the surface.

In the present invention, it is most preferable that the plasma processing be performed using a mixed gas of oxygen gas and argon gas or helium gas. It is desirable to perform the process in-line immediately before forming the inorganic oxide vapor-deposited film on the surface of the polyamide resin film. That is, in the present invention, immediately before forming the inorganic oxide vapor-deposited film on the surface of the polyamide-based resin film, by performing in-line plasma treatment, moisture or dust adhering to the surface of the polyamide-based resin film can be obtained. Plasma treated surface with a thin, highly smooth oxide film formed on the treated surface by causing oxygen molecules activated in the plasma to chemically react with the surface of the polyamide-based resin film. Can be provided. Furthermore, in the present invention, by performing in-line plasma treatment immediately before forming an inorganic oxide vapor-deposited film on the surface of the polyamide-based resin film, for example, hydroxyl groups (-OH Base)
It is also possible to provide a plasma processing surface on which a surface is formed.

Thus, in the present invention, the above-mentioned plasma treatment allows the surface of the polyamide resin film to have an oxide film or a hydroxyl group (—OH group) formed on the plasma treated surface. As will be described later, when the inorganic oxide deposited film is deposited, a very dense inorganic oxide deposited film can be formed, and the adhesion between the polyamide-based resin film and the inorganic oxide deposited film is improved. As a result, the thickness of the deposited film of the inorganic oxide is smaller than the conventional thickness, specifically, 4 nm to 1 nm.
Within the range of 0 nm, an extremely high barrier thin film against oxygen gas or water vapor can be sufficiently formed. In addition, in the present invention, as described above, the inorganic oxide vapor-deposited film may be formed to have a smaller film thickness as compared with the conventional one, and may be a sufficiently high barrier thin film against oxygen gas or water vapor. For example, film winding, printing, laminating
In post-processing such as bag processing or bag making,
Cracks and the like can be prevented from being generated in the above-mentioned inorganic oxide deposited film, and so-called post-processing suitability can be improved. Further, in the present invention, as described above, since the adhesiveness between the polyamide resin film and the inorganic oxide vapor-deposited film is excellent, the laminating suitability of a film or sheet of another resin is also improved. It will improve. Further, in the present invention, since the surface of the polyamide-based resin film is subjected to in-line plasma treatment immediately before the formation of a vapor-deposited film of the inorganic oxide, the production cost of the transparent barrier film is also reduced.
It has the advantage of being extremely superior to other methods and the like.

In the present invention, in the above-mentioned plasma processing, plasma processing conditions are extremely important.
The effect obtained by the condition is completely different. Thus, in the present invention, factors affecting the plasma processing and the chemical reaction include plasma output, gas type, gas supply amount, processing time, and the like. In the present invention, as the plasma treatment, specifically, it is desirable to use a mixed gas of oxygen gas and argon gas or helium gas, and a gas mixture of oxygen gas and argon gas or helium gas. The pressure is preferably about 1 × 10 ^-1 to 1 × 10 ^-10 Torr, more preferably about 1 × 10 ^-4 to 1 × 10 ^-8 Torr, and a pressure of oxygen gas and argon gas or helium gas. The ratio is preferably oxygen gas: argon gas or helium gas = 100: 0 to 30:70, more preferably 90:10 to 70:30 in terms of the partial pressure ratio. About 70 kW, more preferably about 10 to 50 kW is desirable.
The processing speed is preferably about 50 to 800 m / min, more preferably about 200 to 600 m / min. In the above partial pressure ratio of oxygen gas and argon gas or helium gas, when the partial pressure of argon gas or helium gas increases, the number of oxygen molecules activated by plasma decreases, and the argon gas or helium gas is converted to a polyamide gas as a reducing gas. It is not preferable because it reacts with the base resin film to inhibit formation of an oxide film by oxidation of the polyamide resin film or introduction of a hydroxyl group or the like. Further, when the plasma output is 5 kW
If it is less than 10 kW, the activation of oxygen gas is reduced, and it is not preferable because highly active oxygen atoms are not easily generated. If it exceeds 70 kW, furthermore,
If it exceeds 50 kW, the plasma output is too high, which causes a problem that the physical properties of the retort barrier packaging material itself deteriorates due to deterioration of the polyamide resin film, which is not preferable. Further, the above processing speed is less than 50 m / min, and furthermore, 200 m / mi.
When it is less than n, the amount of oxygen plasma with respect to the polyamide resin film is small, and when it exceeds 800 m / min, further, when it exceeds 600 m / min, oxidation of the polyamide resin film proceeds rapidly, This is undesirable because the film becomes porous and the barrier properties are reduced.

In the present invention, as a method for generating plasma in the plasma processing, for example, DC glow discharge, high frequency (Audio Frequ
ency: AF, Radio Frequency: R
F) It can be performed using three types of devices such as discharge and microwave discharge. Thus, in the present invention, it can be usually carried out using a 13.56 MHz high frequency (AF) discharge device.

In the present invention, a plasma-treated surface formed by the above-described plasma treatment on the surface of the polyamide-based resin film immediately before the formation of the inorganic oxide vapor-deposited film may be, for example, an X-ray photoelectron spectrometer (Xray). P
photoelectronSpectroscopy,
XPS), secondary ion mass spectrometer (Secondar)
y Ion Mass Spectroscopy, S
By performing elemental analysis on the plasma-treated surface using a method of performing ion etching in the depth direction or the like using a surface analyzer such as IMS (IMS), as described above, the surface of the polyamide resin film is In addition to removing moisture and dust adhering to the surface, oxygen molecules activated in the plasma cause a chemical reaction with the surface of the polyamide resin film, resulting in a thin and smooth surface. Confirm that the surface is a plasma-treated surface having a high oxide film formed thereon, and that the surface of the polyamide resin film is a plasma-treated surface having, for example, a functional group such as a hydroxyl group (—OH group). Can be done. Specifically, an XPS analysis of the surface to 100 ° was performed under the measurement conditions of MgKα1.2 as the X-ray source, 15 Kv as the X-ray output, and 20 mA, and the formation state of the oxide film was determined by the O / C of the surface. The O / C composition ratio before the treatment and the O / C composition ratio after the treatment are larger after the treatment due to the formation of the oxide. is there. Further, the formation state of a hydroxyl group (—OH group) or the like is O1s
Can be checked by measuring the click, prior to treatment, peak at the position of 532 eV - - the peak of 532 eV position click is not present, by O ₂ plasma treatment, the O1s which means the presence of 0H group A peak occurs at the position of 532 eV.

Next, in the present invention, a vapor-deposited inorganic oxide film having a thickness of 4 nm to 10 nm formed by a chemical vapor deposition method, which constitutes the transparent barrier film, the laminated material and the like according to the present invention, will be described. Examples of the vapor-deposited inorganic oxide deposited film having a thickness of 4 nm to 10 nm by a chemical vapor deposition method include a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method.
It can be formed using a Vapor Deposition method, a CVD method, or the like. In the present invention, specifically, on one side of the polyamide resin film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. Further, a vapor-deposited film of an inorganic oxide such as silicon oxide having a film thickness of 4 nm to 10 nm by using a low-temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. Can be formed. In the above, as the low-temperature plasma generator, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma or the like generator may be used.
In the present invention, in order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

Specifically, a method of forming a deposited film of an inorganic oxide such as silicon oxide having a thickness of 4 nm to 10 nm by the low-temperature plasma chemical vapor deposition method will be described with reference to an example. FIG. 2 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a deposited film of an inorganic oxide by the plasma chemical vapor deposition method. As shown in FIG. 6, in the present invention, the polyamide resin film 1 is fed from the unwinding roll 13 disposed in the vacuum chamber 12 of the plasma enhanced chemical vapor deposition apparatus 11.
And further, the polyamide resin film 1 is
It is conveyed onto the peripheral surface of the cooling / electrode drum 15 at a predetermined speed via the auxiliary roll 14. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatile supply device 18 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and was conveyed onto the peripheral surface of the cooling / electrode drum 15 described above. Plasma is generated on the polyamide-based resin film 1 by the glow discharge plasma 20, and the plasma is irradiated to form a deposited film of an inorganic oxide such as silicon oxide. In the present invention, at this time, the cooling / electrode drum 15 is connected to a power source 21 disposed outside the chamber.
And a predetermined electric power is applied to the cooling / electrode drum 15, and a magnet 22 or the like is arranged in the vicinity of the cooling / electrode drum 15 to promote the generation of plasma. The polyamide resin film 1 on which the vapor-deposited film has been formed is taken up by a winding roll 2 via an auxiliary roll 23.
4 to form a 4 to 10 nm-thick deposited film of an inorganic oxide such as silicon oxide by the plasma enhanced chemical vapor deposition method according to the present invention. In the present invention, as shown in FIG. 6, a plasma generator 26 is provided between the auxiliary roll 14 and the cooling / electrode drum 15, so that the polyamide resin film 1 When the wafer is conveyed onto the peripheral surface of the cooling / electrode drum 15 at a predetermined speed via the auxiliary roll 14, the above-mentioned plasma generator 2 is applied to one surface of the polyamide resin film.
The plasma processing surface can be provided in-line by irradiating the plasma in 6. In the figure, 25 is
Represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby.

In the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, the silicon oxide vapor-deposited film formed above reacts chemically with a monomer gas such as an organic silicon compound and oxygen gas, and the reaction product is formed on one surface of the polyamide resin film. And can form a dense, thin film having high flexibility and the like.
_X (where X represents a number from 0 to 2) is a continuous vapor-deposited film mainly composed of silicon oxide. In view of transparency, barrier properties, and the like, the silicon oxide vapor-deposited film has the general formula SiO _x (where X is 1.3 to 1.9).
Represents the number of It is preferable that the thin film is mainly composed of a silicon oxide deposited film represented by the formula (1). In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has It has a yellow color and poor transparency. Further, the above-described deposited film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or both elements Is contained as a trace constituent element, and the thickness thereof is in the range of 4 nm to 10 nm. Further, the constituent ratio of the essential constituent element and the trace constituent element in the thickness direction is It is changing continuously. Further, when the silicon oxide vapor-deposited film contains a compound composed of carbon, the content of carbon is reduced in the depth direction of the film thickness.

Thus, in the present invention, the above-mentioned deposited film of silicon oxide may be, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec.)
onion Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide film using a method of performing analysis by ion etching in the depth direction or the like using a surface analysis device such as O.I. can do. In the present invention, the thickness of the deposited silicon oxide film is desirably about 4 nm to 10 nm as described above.
It is not preferable because cracks and the like are easily generated in the film, and if the thickness is less than 4 nm, it is difficult to exhibit the barrier effect, which is not preferable.
In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be prepared by a slowing method or the like.

Next, in the present invention, the water-resistant film constituting the transparent barrier film, the laminated material and the like according to the present invention will be described. As the water-resistant film, for example, a resin is mainly composed of a vehicle. A coating film made of a resin composition, or a resin film or sheet film obtained by laminating a resin film or sheet can be used. In the present invention, the formation of the above-mentioned water-resistant film is arbitrarily formed off-line or in-line, for example, to form a deposited film of an inorganic oxide having a thickness of 4 nm to 10 nm by the above-mentioned chemical vapor deposition method. be able to.

A coating film made of a resin composition containing the above resin as a main component of the vehicle will be described. First, as the resin as the main component of the vehicle, for example, a polyethylene resin, a chlorinated polypropylene resin, or the like is used. Polyolefin resin, poly (meth) acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, heat Curable poly (meth) acrylic resin, melamine resin, urea resin, Urethane resin, phenol - Le resins, xylene resins, maleic acid resins, nitrocellulose - scan, ethylcellulose - scan, acetyl butyl cellulose - scan,
Cellulose resins such as ethyloxyethyl cellulose, rubber resins such as chlorinated rubber and cyclized rubber, petroleum resins, rosin,
One or two of natural resins such as casein and other resins
Mixtures of more than one species can be used. Thus, in the present invention, as the resin composition, one or more of the above resins are used as a main component of the vehicle, and
For example, addition of fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, coloring agents, lubricants, antistatic agents, crosslinking agents, etc. It is possible to prepare a resin composition obtained by arbitrarily adding an agent and kneading the mixture sufficiently with a solvent, a diluent or the like. Next, in the present invention, as the coating film, a resin composition as described above may be used, for example, a spray coat, a dip coat, a kiss roll coat, a reverse roll coat, a curtain floor coat. -Coat, squeeze roll, gravure roll
Coating is performed by using a known coating method such as coating, spin coating, or the like, and then drying is performed to form a coating film. In the above, the thickness of the coating film is 0.5 μm in a dry state.
It is desirably about m to 300 μm, preferably about 5 μm to 50 μm.

The resin film or sheet obtained by laminating the above resin film or sheet will be described. First, as the resin film or sheet, for example, low-density polyethylene, medium Density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer,
Poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin Resin, polycarbonate-based resin, polyvinyl alcohol-based resin, saponified ethylene-vinyl acetate copolymer, fluorine-based resin, diene-based resin,
It can be arbitrarily selected from films or sheets of various resins such as polyacetal resins, polyurethane resins, cellulose resins such as nitrocellulose, and others. In the present invention, the above film or sheet
Any of unstretched, stretched uniaxially or biaxially can be used. The thickness is arbitrary, but can be selected from a range of about several μm to 300 μm, preferably about 5 μm to 100 μm. Next, in the present invention, as a method of laminating a resin film or sheet as described above, a method of laminating a usual packaging material, for example, a wet lamination method, a dry lamination method, a solventless method Lamination can be carried out by using a die dry lamination method, an extrusion lamination method, a T-die extrusion lamination method, a co-extrusion lamination method, or other lamination methods. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a known pre-treatment such as corona treatment, ozone treatment, framing treatment, etc. can be optionally performed, For example, anchor coating agents such as polyester, isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, and polyacetic acids Vinyl type, cellulo
A laminating adhesive such as a water-based or other laminating agent can be optionally used.

Further, in the present invention, the water-resistant film is, for example, parallel to a chemical vapor deposition apparatus for forming a 4 to 10 nm-thick inorganic oxide vapor-deposited film by the chemical vapor deposition method described above. A roll-up vacuum vapor deposition device and the like are provided in parallel. Can be formed into a water-resistant film by forming a vapor-deposited thin film layer. In the above, the organic compound forming the vapor-deposited thin film layer of the organic compound is mainly a compound composed of carbon and hydrogen, and further, for example, may contain elements such as oxygen and nitrogen, and further, A metal element or the like may be contained, and an organic compound that is liquid or solid at room temperature can be used for forming the vapor-deposited thin film layer. As the organic compound, for example, a mixture of one or more of natural or synthetic resins, natural or synthetic rubbers, or natural or synthetic waxes, and a mixture of one or more of lubricants are also used. be able to. Specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, methylpentene resin, polybutene resin, polystyrene resin, poly (meth) acrylic resin, polyacrylnitrile resin, polycarbonate -Resin, phenol resin, furan resin, ketone resin, xylene resin,
Melamine-based resins, urea-based resins, aniline-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, synthetic resins such as others, rosin, shellac, natural resins such as others, ethylene-propylene rubber, butyl rubber,
Synthetic rubbers such as nitrile rubber, acrylic rubber, silicone rubber, etc., natural rubbers such as raw rubber, paraffin wax, microcrystalline wax, candelilla wax, carnauba wax, montan wax, polyolefin wax, microcrystalline wax, etc. And other lubricants such as natural or synthetic waxes, silicone oils, fluorine oils, polyalkylnaphthalene oils, polyalkylphthalate oils, polyphenyl ether oils, petroleum fractions, mineral oils, etc. Can be used. In the present invention, the above organic compounds can be used alone or as a mixture of two or more.

Next, in the present invention, the primer agent layer constituting the laminated material will be described.
As the agent layer, first, a polyurethane-based resin is used as a main component of a vehicle, and a silane coupling agent is used in an amount of about 0.05 to 10% by weight, preferably 0.1% by weight, based on 1 to 30% by weight of the polyurethane-based resin. ~ 5% by weight, filler 0.1 ~
It is added in an amount of about 20% by weight, preferably about 1 to 10% by weight, and if necessary, a stabilizer, a curing agent, a crosslinking agent,
Lubricants, UV absorbers, and other additives such as other optional additives, solvents, diluents and the like are added and mixed well to adjust the polyurethane-based resin composition. It is used, for example, by a roll coating, a gravure coating, a knife coating, a dip coating, a spray coating, or another coating method. And then,
The primer film according to the present invention can be formed by drying the coating film to remove the solvent, diluent, and the like, and, if necessary, performing aging treatment and the like. In the present invention, the thickness of the primer layer is preferably, for example, about 0.1 g / m ^{2 to} 1.0 g / m ² (dry state). Thus, in the present invention, the primer agent layer as described above allows the inorganic oxide vapor-deposited film to be heat-sealed.
And the elongation of the primer agent layer are improved, for example, by laminating,
Alternatively, it is intended to improve the suitability for post-processing such as bag making, and to prevent the occurrence of cracks and the like in the deposited film of the inorganic oxide during the post-processing.

In the above description, as the polyurethane resin constituting the polyurethane resin composition, for example, a polyurethane resin obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound can be used. Specifically, for example, tolylene diisocyanate-
Aromatic polyisocyanate such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate
And polyfunctional isocyanates such as aliphatic polyisocyanates such as xylylene diisocyanate and hydroxyl group-containing compounds such as polyether polyols, polyester polyols, polyacrylate polyols and the like. One- or two-component curable polyurethane resins obtained by the reaction can be used. Thus, in the present invention, by using the above-mentioned polyurethane-based resin, it is possible to improve the tight adhesion between the inorganic oxide vapor-deposited film and the heat-sealing resin layer and to improve the primer agent layer. In this case, the elongation of the film is improved, for example, the suitability for post-processing such as laminating or bag-making is improved, and the occurrence of cracks or the like in the deposited film of the inorganic oxide during the post-processing is prevented.

Next, in the above, as the silane coupling agent constituting the polyurethane resin composition,
Binary reactive organofunctional silane monomers can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy)
Silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N -Β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, aqueous solution of γ-aminopropylsilicone, etc. Seeds or more can be used.

The silane coupling agent described above hydrolyzes a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, to form a silanol group (SiOH). The metal constituting the vapor-deposited film of the inorganic oxide, or an active group on the surface of the vapor-deposited film of the inorganic oxide, for example, a functional group such as a hydroxyl group, by some action, for example, causing a reaction such as a dehydration condensation reaction, A silane coupling agent is modified on the surface of the inorganic oxide vapor-deposited film by a covalent bond or the like, and a strong bond is formed on the surface of the inorganic oxide vapor-deposited film of the silanol group itself by adsorption or hydrogen bonding. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on a thin film of the silane coupling agent. Reacts with substances constituting the adhesive layer for coating, the anchor coating agent layer, other layers, etc. to form a strong bond, and further forms the above-mentioned printed pattern layer, adhesive layer for laminating, Anchor-co-
The heat-sealing resin layer is firmly and tightly adhered to the heat-sealing resin layer via the agent layer or the like, thereby increasing the laminating strength.
In the present invention, a strong laminated structure having high laminate strength can be formed. In the present invention, the inorganic and organic properties of the silane coupling agent are utilized, and the heat is applied through a vapor-deposited inorganic oxide film and a printed pattern layer, an adhesive layer or an anchor coating agent layer. Improves the tight adhesion with the sealable resin layer, thereby improving the laminating properties.
And to enhance the strength of the device.

Next, in the present invention, examples of the filler constituting the polyurethane resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used. Thus, the above filler is
The viscosity and the like of the polyurethane resin composition liquid are adjusted to improve the coating suitability, and the polyurethane resin as a binder resin is bonded via a silane coupling agent to improve the cohesive force of the coating film. It is to let.

Next, in the present invention, the adhesive layer for laminating constituting the laminated material will be explained.
Polyvinyl acetate adhesives, homopolymers such as ethyl, butyl and 2-ethylhexyl acrylates, or polyacrylate adhesives comprising copolymers of these with methyl methacrylate, acrylonitrile, styrene, etc. , Cyanoacrylate adhesives, ethylene copolymer adhesives composed of copolymers of ethylene with monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives, polyester-based adhesives Adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, reactive (meth) Acrylic adhesive, chloroprene rubber, nitrile rubber, styrene
Adhesives such as a rubber-based adhesive made of butadiene rubber, a silicone-based adhesive, an inorganic adhesive made of an alkali metal silicate, a low-melting glass, and the like can be used. The composition system of the above-mentioned adhesive may be any composition form such as aqueous type, solution type, emulsion type, dispersion type, and the like, and its properties are film sheet, powder,
Any form such as a solid form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a hot melt type, and a hot pressure type. The above-mentioned adhesive is, for example, a roll coat method, a gravure roll coat.
Coating method such as coating method, kiss coating method, etc., or
It can be applied by a printing method or the like, and the coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, the anchor coating agent layer constituting the laminated material will be described. The anchor coating agent constituting the anchor coating agent layer is, for example, an alkyl titanate. Organotitanium, isocyanate, polyethyleneimine, polybutadiene, etc.
Various other aqueous or oil-based anchor coating agents can be used. The above-mentioned anchor coating agents include, for example, roll coat, gravure roll coat, kisco-coat.
Coating can be performed by using a coating method such as coating, etc., and the coating amount is 0.1 to
5 g / m ² (dry state) is desirable.

Next, in the present invention, the innermost layer of the laminated material,
Alternatively, as the heat-sealing resin constituting the heat-sealing resin layer forming the outermost layer, a resin film or sheet which can be melted by heat and fused to each other can be used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-α-olefin copolymer polymerized using a metallocene catalyst, polypropylene , Ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene Polyolefins such as copolymers, methylpentene polymers, polybutene polymers, polyethylene or polypropylene -Modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin obtained by modifying resin based on unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. And films or sheets of resins such as polyvinyl chloride resins and others. Thus,
The above film or sheet can be used in the form of a coating film of a composition containing the resin.
As the thickness of the film or film or sheet,
It is preferably about 5 μm to 300 μm, more preferably about 10 μm.
μm to 100 μm is desirable.

By the way, in the present invention, a method for producing a laminate according to the present invention using the above-mentioned materials includes, for example, First, the above-mentioned primer agent layer is formed, and then the above-mentioned adhesive layer for laminating is formed on the surface of the primer agent layer, and thereafter, the above-mentioned primer agent layer and the adhesive for laminating are formed. By laminating a heat-sealing resin film or sheet constituting the heat-sealing resin layer by a dry laminating lamination method via an agent layer or the like, the laminated material according to the present invention is obtained. Can be manufactured. Alternatively, in the present invention, for example, on the surface of the inorganic oxide deposited film of the above-mentioned transparent barrier film, first,
Forming the above-mentioned primer agent layer,
The above-mentioned anchor coating agent layer is formed on the surface of the agent layer, and thereafter, a heat-sealing resin layer is formed via the primer agent layer and the anchor coating agent layer. The laminated material according to the present invention can be manufactured by laminating the heat-sealing resin to be melt-extruded using a laminating lamination method.

Further, in the present invention, the base film layer constituting the laminate according to the present invention will be described. The base film constituting the base film layer is, for example, a case where a packaging container is formed. Since it becomes a basic material, it has excellent properties in mechanical, physical, chemical, etc., and in particular, a resin film or sheet having strength, toughness, and heat resistance. Can be used, specifically, for example, polyester-based resin, polyamide-based resin, polyaramid-based resin,
A film or sheet of a tough resin such as a polyolefin resin, a polycarbonate resin, a polystyrene resin, a polyacetal resin, a fluorine resin, or the like can be used. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm. In the present invention, the base film as described above is subjected to, for example, front printing or back printing by printing a desired printing pattern such as a character, a figure, a symbol, a picture, or a pattern by a normal printing method. It may be.

Next, in the present invention, as a material constituting the base film, for example, various paper base materials constituting a paper layer can be used. The paper base material is provided with moldability, bending resistance, rigidity and the like. For example, a strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard , A paper base material such as processed paper, and the like can be used. 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 . Needless to say, in the present invention, a paper base constituting the paper layer and various resin films or sheets as the base films mentioned above can be used in combination.

Next, in the present invention, as a material constituting the laminate according to the present invention, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low High-density polyethylene, polypropylene, a film or sheet of a resin such as an ethylene-propylene copolymer, or polyvinylidene chloride having a barrier property against oxygen, water vapor, and the like;
Film or sheet of resin such as polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, light-shielding obtained by adding a colorant such as pigment to the resin and other desired additives and kneading to form a film. Various colored resin films or sheets having properties can be used. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but usually 5 μm to 300 μm.
And more preferably about 10 μm to 100 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. A material that satisfies the above conditions can be arbitrarily selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Next, a method for producing a laminated material 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, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film, and for example, an isocyanate-based (urethane) Series), polyethyleneimine series, polybutadiene series, organic titanium series etc.
Known pretreatments such as coating agents or adhesives for laminating such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., anchor coating Agents, adhesives and the like can be used.

In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminate according to the present invention. Thus, as the above-mentioned printed pattern layer, one or two or more of ordinary ink vehicles are used.
As a main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, a UV absorber, a curing agent,
One or two or more additives such as a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like are optionally added, and further, a coloring agent such as a dye or a pigment is added. To prepare an ink composition, and then using the ink composition, for example, using a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. Then, a desired printed pattern composed of characters, figures, symbols, patterns and the like can be printed on the above-mentioned coating thin film to form a printed pattern layer according to the present invention.

In the present invention, as the primer agent layer provided on the surface of the above-mentioned inorganic oxide vapor-deposited film, in addition to the above-mentioned primer agent layer made of the polyurethane resin segment, for example, Polyolefin resins such as polyester resins, polyamide resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene aliha polypropylene, or copolymers or modified resins thereof, cellulose The primer agent layer can be formed by using a resin composition containing a base resin or the like as a main component of the vehicle. In the present invention, a primer coating agent layer is formed by coating using a coating method such as roll coating, gravure coating, kiss coating, or the like. Therefore, the coating amount is 0.1
It is preferably about 10 to 10 g / m ² (dry state).

Next, in the present invention, a method for producing a bag or a box using the above-described laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using the laminated material manufactured by the above method, the heat-sealing film of the inner layer is opposed to the surface, and the heat-sealing film is folded or the two sheets are overlapped, and the peripheral edge is further heated. -A bag can be formed by sealing and providing a seal portion. Thus, as a bag-making method, the above-mentioned laminated material is bent with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further sealed with, for example, a side sheet. Seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seal type),
Heat seals such as pleated seal type, flat bottom seal type, square bottom seal type, etc., to form packaging containers of various forms according to the present invention. Can be manufactured. In addition, for example, a self-standing packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the above-described laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotating roll seal,
It can be carried out by a known method such as a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal, and the like. In the present invention, a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container containing a paper substrate as the packaging container, for example, a laminated material in which a paper substrate is laminated is produced as a laminated material, and a desired paper container is produced therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head, and the like are manufactured using the blank plate to manufacture, for example, a brick-type, flat-type or gable-top type liquid paper container. be able to. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

In the present invention, the packaging container manufactured as described above can be used for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other articles. It is used for filling and packaging. Thus, in the present invention, particularly, for example, soy sauce, source,
Small bags for liquids for filling and packaging soups, bags for soft packaging for filling and packaging raw confectionery, or curries, stews, soups
It is useful as a packaging container for filling and packaging liquid foods or drinks containing water or the like, such as soft packaging bags for filling and packaging boil or retort foods and the like such as bottles, hamburgers and the like.

[0049]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 (1). A 15 μm-thick biaxially stretched nylon 6 film was used as a base material, and was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. Provided. (Plasma treatment conditions) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Plasma gas: helium gas (9.4 slm) Plasma supply power: 15 kW Treatment surface: Corona treatment surface On the plasma-treated surface of the axially stretched nylon 6 film, a vapor-deposited silicon oxide thin film having a thickness of 8 nm was formed in-line under the following plasma-enhanced chemical vapor deposition conditions. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: sl)
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar Line speed; 300 m / min Power; 35 kW Immediately after the formation, on the surface of the deposited silicon oxide film, using a glow discharge plasma generator, power: 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit) : Slm) and a mixed gas pressure of 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
A plasma treatment with an argon mixed gas was performed to form a plasma treatment surface in which the surface tension of the surface of the deposited silicon oxide film was improved by 54 dyne / cm or more, thereby producing a transparent barrier film according to the present invention. (2). Next, on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film produced in the above (1), an initial condensate of a polyurethane resin, an epoxy silane coupling agent (8.0% by weight). And an anti-blocking agent (1.0% by weight) were added and kneaded well to use a primer composition, which was then subjected to a gravure roll coating method to obtain a film thickness of 0.4 g / m ² (dry To form a primer agent layer. Further, a two-component curable polyurethane-based laminating adhesive is used on the surface of the primer layer formed as described above, and the adhesive is applied to the film by a gravure roll coating method in the same manner as described above. 0g
/ M ² (dry state) to form an adhesive layer for lamination. Next, a linear low-density polyethylene film having a thickness of 50 μm is overlaid on the surface of the adhesive layer for laminating formed as described above, with the corona-treated surface of the film facing the corona-treated surface. Thus, a laminated material according to the present invention was manufactured. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The curry is filled and packaged through the opening in the three-sided seal-type soft packaging bag produced above, and then the opening is sealed.
An upper seal portion was formed by sealing to produce a packaged semi-finished product, and the packaged semi-finished product was further boiled at 90 ° C. for 30 minutes to produce a packaged product. The packaged product produced above has excellent barrier properties against oxygen gas, water vapor, etc., and also has excellent laminate strength and the like, and can withstand distribution in the market, and
It was excellent in storage and preservation.

Embodiment 2 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, a plasma-treated surface was formed on one surface of the biaxially stretched nylon 6 film in exactly the same manner as in Example 1 above. 8 nm thick on the treated surface
A silicon oxide deposited film was formed, and a plasma treated surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more was formed to produce a transparent barrier film according to the present invention. . (2). Next, a primer agent layer was formed on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film produced in the above (1), in exactly the same manner as in Example 1 above. Next, on the surface of the primer layer formed as described above, a two-component curable urethane-based anchor coating agent was used. The coating was performed so as to be 1 g / m ² (dry state) to form an anchor coating agent layer. Next, a linear low-density polyethylene resin was used on the surface of the anchor coating agent layer formed above and melt-extruded using an extruder to obtain a linear low-density polyethylene resin having a thickness of 50 μm. The layers were extruded and laminated to produce a laminate according to the present invention. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packaged. Thereafter, the opening is heat-sealed to form an upper seal. Manufactured liquid sachet packaging products. The packaged product produced above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminating strength, etc., withstanding distribution in the market, and excellent in storage and preservation. .

Embodiment 3 (1). A 15-μm-thick biaxially stretched nylon 6 film was used as a substrate, and a resin composition containing a thermosetting acrylic resin as a main component of a vehicle was coated on one surface thereof by a kiss roll coating method. The coating was then dried to form a coating film having a thickness of 1 μm. Next, a 15 μm-thick biaxially stretched nylon 6 film having a coating film formed thereon was used, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Processing was performed to provide a plasma processing surface. (Plasma processing conditions) Degree of vacuum in vacuum chamber: 7.
0 × 10 ⁻⁶ mbar Plasma gas: mixed gas of helium and oxygen (1 / 9s)
Im) Plasma supply power: 2 kW Treatment surface: Corona treatment surface Next, on the plasma treatment surface of the biaxially stretched nylon film having the plasma treatment surface formed thereon, an in-line 8 nm-thickness film was formed under the following plasma chemical vapor deposition conditions. A deposited thin film of silicon oxide was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: sl)
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar Line speed; 300 m / min Power; 35 kW Immediately after the formation, on the surface of the deposited silicon oxide film, using a glow discharge plasma generator, power: 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit) : Slm) and a mixed gas pressure of 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
The transparent barrier film according to the present invention was manufactured by performing a plasma treatment with an argon mixed gas to form a plasma treated surface in which the surface tension of the surface of the deposited silicon oxide film was improved by 54 dyne / cm or more. (2). Next, on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film produced in the above (1), an initial condensate of a polyurethane resin, an epoxy silane coupling agent (8.0% by weight). And an anti-blocking agent (1.0% by weight) were added and kneaded well to use a primer composition, which was then subjected to a gravure roll coating method to obtain a film thickness of 0.4 g / m ² (dry To form a primer agent layer. Further, a two-component curable polyurethane-based laminating adhesive is used on the surface of the primer layer formed as described above, and the adhesive is applied to the film by a gravure roll coating method in the same manner as described above. 0g
/ M ² (dry state) to form an adhesive layer for lamination. Next, a linear low-density polyethylene film having a thickness of 50 μm is overlaid on the surface of the adhesive layer for laminating formed as described above, with the corona-treated surface of the film facing the corona-treated surface. Thus, a laminated material according to the present invention was manufactured. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The curry is filled and packaged through the opening in the three-sided seal-type soft packaging bag produced above, and then the opening is sealed.
An upper seal portion was formed by sealing to produce a packaged semi-finished product, and the packaged semi-finished product was further boiled at 90 ° C. for 30 minutes to produce a packaged product. The packaged product produced above has excellent barrier properties against oxygen gas, water vapor, etc., and also has excellent laminate strength and the like, and can withstand distribution in the market, and
It was excellent in storage and preservation.

Embodiment 4 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, a coating film was formed on one surface of the biaxially stretched nylon 6 film in exactly the same manner as in Example 3 above, and the other side was formed. Form a plasma treated surface on the surface,
Further, a vapor-deposited silicon oxide film having a thickness of 8 nm is formed on the surface of the plasma-treated surface, and a plasma-treated surface is formed by increasing the surface tension of the vapor-deposited silicon oxide film surface by at least 54 dyne / cm. Thus, a transparent barrier film according to the present invention was produced. (2). Next, a primer agent layer was formed on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film produced in the above (1), in exactly the same manner as in Example 1 above. Next, on the surface of the primer layer formed as described above, a two-component curable urethane-based anchor coating agent was used. The coating was performed so as to be 1 g / m ² (dry state) to form an anchor coating agent layer. Next, a linear low-density polyethylene resin was used on the surface of the anchor coating agent layer formed above and melt-extruded using an extruder to obtain a linear low-density polyethylene resin having a thickness of 50 μm. The layers were extruded and laminated to produce a laminate according to the present invention. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packaged. Thereafter, the opening is heat-sealed to form an upper seal. Manufactured liquid sachet packaging products. The packaged product produced above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminating strength, etc., withstanding distribution in the market, and excellent in storage and preservation. .

Comparative Example 1 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Then, a deposited film of silicon oxide having a thickness of 20 nm was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: sl)
m) Ultimate pressure: 5.0 × 10 ⁻⁵ mbar Film forming pressure: 7.0 × 10 ⁻² mbar Line speed: 150 m / min Power: 35 kW Next, a silicon oxide vapor deposition film having a film thickness of 20 nm was formed as described above. Immediately after the formation, a glow discharge plasma generator was used to apply a power of 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit) to the surface of the deposited silicon oxide film. : Slm) and a mixed gas pressure of 6
× 10 ⁻⁵ Torr, processing speed 420 m / min, oxygen /
Plasma treatment with an argon mixed gas was performed to form a plasma treated surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more, thereby producing a transparent barrier film. (2). Next, on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film produced in the above (1), an initial condensate of a polyurethane resin, an epoxy silane coupling agent (8.0% by weight). And an anti-blocking agent (1.0% by weight) were added and kneaded well to use a primer composition, which was then subjected to a gravure roll coating method to obtain a film thickness of 0.4 g / m ² (dry To form a primer agent layer. Further, a two-component curable polyurethane-based laminating adhesive is used on the surface of the primer layer formed as described above, and the adhesive is applied to the film by a gravure roll coating method in the same manner as described above. 0g
/ M ² (dry state) to form an adhesive layer for lamination. Next, a linear low-density polyethylene film having a thickness of 50 μm is overlaid on the surface of the laminating adhesive layer formed above with the corona-treated surface of the polyethylene film facing the corona-treated surface. Thus, a laminated material was manufactured. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The curry is filled and packaged through the opening in the three-sided seal-type soft packaging bag produced above, and then the opening is sealed.
An upper seal portion was formed by sealing to produce a packaged semi-finished product, and the packaged semi-finished product was further boiled at 90 ° C. for 30 minutes to produce a packaged product.

Comparative Example 2 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, a corona-treated surface of the biaxially stretched nylon 6 film having a thickness of 20 n
A silicon oxide deposited film was formed, and a plasma treated surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more was formed to produce a transparent barrier film. (2). Next, on the plasma-treated surface of the deposited silicon oxide film of the transparent barrier film produced in the above (1), an initial condensate of a polyurethane resin, an epoxy silane coupling agent (8.0% by weight). And an anti-blocking agent (1.0% by weight) were added and kneaded well to use a primer composition, which was then subjected to a gravure roll coating method to obtain a film thickness of 0.4 g / m ² (dry To form a primer agent layer. Further, on the surface of the primer layer formed as described above, a two-part curable urethane-based anchor coating agent was used. 1g / m
² Anchor by coating so that it is (dry)
A coating agent layer was formed. Next, the anchor formed above is used.
A linear low-density polyethylene resin was used for the coating agent layer surface, and was extruded using an extruder to give a thickness of 50%.
A linear low-density polyethylene resin layer of μm was extruded and laminated by lamination to produce a laminated material. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packed, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

Comparative Example 3 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used. The film was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. Then, a deposited film of silicon oxide having a thickness of 8 nm was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: sl)
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar Line speed; 300 m / min Power; 35 kW Immediately after the formation, on the surface of the deposited silicon oxide film, using a glow discharge plasma generator, power: 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit) : Slm) and a mixed gas pressure of 6
X10 ^-5 Tool, treatment speed 420m / min, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the surface of the deposited silicon oxide film was improved by 54 dyne / cm or more, thereby producing a transparent barrier film. (2). Next, a two-component curable polyurethane-based laminating adhesive was used on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film produced above, and this was applied by a gravure roll coating method. The coating was performed so as to have a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for laminating. Next, a linear low-density polyethylene film having a thickness of 50 μm is overlaid on the surface of the laminating adhesive layer formed above with the corona-treated surface of the polyethylene film facing the corona-treated surface. do it,
A laminated material was manufactured. (3). Next, two sheets of the laminated material manufactured as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is heat sealed three-way. A three-way seal-type soft packaging pouch having a seal portion and an opening above was manufactured. Soy sauce is filled and packaged from the opening in the three-sided seal-type soft sachet prepared above, and then the opening is heat-sealed to form an upper seal. A liquid sachet packaging product was manufactured.

Comparative Example 4 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, the corona-treated surface of the biaxially stretched nylon 6 film was 8 nm thick in exactly the same manner as in Comparative Example 3 above.
Was formed, and further, a plasma treated surface was formed in which the surface tension of the surface of the deposited silicon oxide film was improved by 54 dyne / cm or more to produce a transparent barrier film. Next, a two-component curable urethane-based anchor coating agent was used on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film produced above, and this was applied by a gravure roll coating method. The coating was performed so as to have a thickness of 0.1 g / m ² (dry state) to form an anchor coating agent layer. Next, a linear low-density polyethylene resin was used on the surface of the anchor coating agent layer formed above and melt-extruded using an extruder to obtain a linear low-density polyethylene resin having a thickness of 50 μm. The layers were extruded and laminated to produce a laminate. (2). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packaged. Thereafter, the opening is heat-sealed to form an upper seal. Manufactured liquid sachet packaging products.

Comparative Example 5 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, a plasma-treated surface was formed on one of the surfaces in exactly the same manner as in Example 1 above. Was formed, and a plasma-treated surface was formed on the surface of the silicon oxide film to produce a transparent barrier film. Next, a two-component curable polyurethane-based laminating adhesive was used on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film produced above, and this was applied by a gravure roll coating method. ,
An adhesive layer for lamination was formed by coating so as to have a thickness of 4.0 g / m ² (dry state). Next, a linear low-density polyethylene film having a thickness of 50 μm is overlaid on the surface of the laminating adhesive layer formed above with the corona-treated surface of the polyethylene film facing the corona-treated surface. Thus, a laminated material was manufactured. (2). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The curry is filled and packaged through the opening in the three-sided seal-type soft packaging bag produced above, and then the opening is sealed.
An upper seal portion was formed by sealing to produce a packaged semi-finished product, and the packaged semi-finished product was further boiled at 90 ° C. for 30 minutes to produce a packaged product.

Comparative Example 6 (1). Using a biaxially stretched nylon 6 film having a thickness of 15 μm, a plasma-treated surface was formed on one of the surfaces in exactly the same manner as in Example 2 described above. Was formed, and a plasma-treated surface was formed on the surface of the silicon oxide film to produce a transparent barrier film. Next, a two-component curable urethane-based anchor coating agent was used on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film produced above, and this was applied by a gravure roll coating method. The coating was performed so as to have a thickness of 0.1 g / m ² (dry state) to form an anchor coating agent layer. Next, a linear low-density polyethylene resin was used on the surface of the anchor coating agent layer formed above and melt-extruded using an extruder to obtain a linear low-density polyethylene resin having a thickness of 50 μm. The layers were extruded and laminated to produce a laminate. (2). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packaged. Thereafter, the opening is heat-sealed to form an upper seal. Manufactured liquid sachet packaging products.

Comparative Example 7 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used as a base material, and a coating film was formed on one of the surfaces, and plasma was Forming a treated surface, further forming a silicon oxide deposited film on the surface of the plasma treated surface,
A plasma-treated surface was formed on the surface of the deposited silicon oxide film to produce a transparent barrier film. Next, a two-component curable polyurethane-based laminating adhesive was used on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film. An adhesive layer for lamination was formed by coating so as to have a thickness of 4.0 g / m ² (dry state). Next, a linear low-density polyethylene film having a thickness of 50 μm is overlaid on the surface of the laminating adhesive layer formed above with the corona-treated surface of the polyethylene film facing the corona-treated surface. Thus, a laminated material was manufactured. (2). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The curry is filled and packaged through the opening in the three-sided seal-type soft packaging bag produced above, and then the opening is sealed.
An upper seal portion was formed by sealing to produce a packaged semi-finished product, and the packaged semi-finished product was further boiled at 90 ° C. for 30 minutes to produce a packaged product.

Comparative Example 8 (1). A 15 μm-thick biaxially stretched nylon 6 film was used as a base material. A coating film was formed on one surface of the film and a plasma film was formed on the other surface in exactly the same manner as in Example 4 above. Forming a treated surface, further forming a silicon oxide deposited film on the surface of the plasma treated surface;
A plasma-treated surface was formed on the surface of the deposited silicon oxide film to produce a transparent barrier film. Next, a two-component curable urethane-based anchor coating agent was used on the plasma-treated surface of the silicon oxide vapor-deposited film of the transparent barrier film, and this was applied to the film by a gravure roll coating method. Thickness 0.
The coating was performed so as to be 1 g / m ² (dry state) to form an anchor coating agent layer. Next, on the anchor-coating agent layer surface formed above, a linear low-density polyethylene resin was used, and this was melt-extruded using an extruder,
A 50 μm-thick linear low-density polyethylene resin layer was extruded and laminated to produce a laminated material. (2). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packaged. Thereafter, the opening is heat-sealed to form an upper seal. Manufactured liquid sachet packaging products.

Comparative Example 9 (1). Using nylon 6 and nylon MXD-6,
The nylon MXD-6 is used as an intermediate layer, and the first layer is 5 μm in thickness, the intermediate layer is 5 μm in thickness, and the second layer is 5 μm in thickness.
To form a co-extruded multilayer nylon film. (2). Next, on one side of the co-extruded multilayer nylon film formed in the above (1), a two-component curable polyurethane-based laminating adhesive is used, and this is applied by a gravure roll coating method. An adhesive layer for lamination was formed by coating so as to have a thickness of 4.0 g / m ² (dry state). Next, a 50 μm-thick linear low-density polyethylene film was laminated on the laminating adhesive layer surface formed above with the corona-treated surface facing the linear low-density polyethylene film,
Thereafter, the two were laminated by dry lamination to produce a laminated material. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The curry is filled and packaged through the opening in the three-sided seal-type soft packaging bag produced above, and then the opening is sealed.
An upper seal portion was formed by sealing to produce a packaged semi-finished product, and the packaged semi-finished product was further boiled at 90 ° C. for 30 minutes to produce a packaged product.

Comparative Example 10 (1). Using nylon 6 and nylon MXD-6,
The nylon MXD-6 is used as an intermediate layer, and the first layer is 5 μm in thickness, the intermediate layer is 5 μm in thickness, and the second layer is 5 μm in thickness.
To form a co-extruded multilayer nylon film. (2). Next, on one surface of the co-extruded multilayer nylon film formed in the above (1), a two-component curable urethane-based anchor coating agent was used, and this was applied by a gravure roll coating method. An anchor coat agent layer was formed by coating so as to have a thickness of 0.1 g / m ² (dry state). Next, a linear low-density polyethylene resin was used on the surface of the anchor coating agent layer formed above and melt-extruded using an extruder to obtain a linear low-density polyethylene resin having a thickness of 50 μm. The layers were extruded and laminated to produce a laminate. (3). Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the linear low-density polyethylene films are superposed on each other, and then the outer peripheral edge is three-sided heat-sealed. A three-way seal-type soft packaging bag having a seal portion and an opening above was manufactured. The three-way seal-type soft packaging bag produced above is filled with soy sauce through its opening and then packaged. Thereafter, the opening is heat-sealed to form an upper seal. Manufactured liquid sachet packaging products.

EXPERIMENTAL EXAMPLE 1 In Examples 1 to 4 above, a transparent barrier film provided with a primer agent layer and a laminated material were compared. Comparative Examples 3 to 8 provided with layers and laminated materials
Is for the transparent barrier film and the laminate
Comparative Examples 9 to 10 are co-extruded multilayer nylon films,
And about the laminated material, the oxygen permeability and the water vapor permeability were measured. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is a condition of temperature of 40 ° C and humidity of 90% RH in the United States,
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. The above measurement results are shown in Table 1 below.

[0064] In Table 1 above, the unit of oxygen permeability is [cc / m
² / day · 23 ° C. · 90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 10
0% RH].

As is evident from the measurement results shown in Table 1 above, the transparent barrier film according to the present invention and the laminated material using the same have a small thickness even if the inorganic oxide deposited film is thin.
It is excellent in oxygen barrier properties, water vapor barrier properties, etc., and particularly excellent in oxygen barrier properties, and can be sufficiently used as a barrier packaging material.

Experimental Example 2 Laminate strength was measured for the laminated materials manufactured in Examples 1 to 4 and Comparative Examples 1 to 10. This was measured by cutting a 15 mm wide strip of the laminated material, performing T-peeling with Tensilon at a peeling speed of 300 mm / min.
The above measurement results are shown in Table 2 below.

[0067]

As is evident from the results shown in Table 2 above, the laminated material according to the present invention has excellent laminating strength even when the inorganic oxide vapor-deposited film is thin, and is sufficiently used as a packaging material. Gain.

EXPERIMENTAL EXAMPLE 3 The surface of the transparent barrier film produced in Examples 1 to 4 and Comparative Examples 1 to 8 on which the inorganic oxide was deposited, and the co-extruded multilayer nylon produced in Comparative Examples 9 to 10 A desired printing pattern was printed on one surface of the film with a two-color gravure printing machine, and the oxygen permeability and water vapor permeability of the printed transparent barrier film and the co-extruded multilayer nylon film were measured. The oxygen permeability and the water vapor permeability were measured in the same manner as described above. The results of the above measurements are shown in Table 3 below.

[0070] In Table 3 above, the unit of oxygen permeability is [cc / m
² / day · 23 ° C. · 90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 10
0% RH].

As is evident from the measurement results shown in Table 3 above, the transparent barrier film according to the present invention did not show any deterioration in oxygen barrier properties even after printing.
It can be sufficiently used as a barrier packaging material.

Experimental Example 4 The three-sided seal type flexible packaging bag manufactured using the laminated material manufactured in Examples 1 and 3 and Comparative Examples 1, 3, 5, 7, and 9 The opening is filled with water as a content, and then the opening is heat-sealed to form an upper seal to produce a packaged semi-finished product.
It was placed in water at 0 ° C. and 100 ° C. and boiled for 30 minutes to produce a packaged product. Thereafter, the contents were taken out and dried, and then the oxygen permeability and the laminate strength of the laminated material were measured. The oxygen permeability and the laminating intensity were measured in the same manner as described above. The above measurement results are shown in Table 4 below.

[0073] In Table 1 above, the unit of oxygen permeability is [cc / m
² / day · 23 ° C. · 90% RH], and the unit of the laminating strength is [kg / 15 mm width].

As is clear from the measurement results shown in Table 4 above, the laminated material produced by using the transparent barrier film according to the present invention, and the packaging bag produced by using the laminated material were: Even after the boil treatment, even when the deposited film of silicon oxide is thin, deterioration of the oxygen barrier property or the like is not recognized,
Further, it has excellent laminating strength and can be sufficiently used as a packaging material.

[0075]

As is apparent from the above description, the present invention uses a polyamide resin film as a base film for vapor deposition, and thus, one side of the polyamide resin film is subjected to plasma treatment. The surface is further provided, and a vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the surface of the plasma-treated surface by a chemical vapor deposition method in a thickness of 4 nm to 10 nm to produce a transparent barrier film. Alternatively, a water-resistant film is provided in advance on one surface of the polyamide-based resin film, a plasma-treated surface is first provided on the other surface, and a chemical vapor deposition is further provided on the plasma-treated surface. A deposited film of an inorganic oxide such as silicon oxide by
Formed in the range of 10 nm to produce a transparent barrier film, and then to the transparent barrier film produced above,
For example, a heat-sealing resin layer, a base film layer, and the like are laminated to produce a packaging laminate, and further, the packaging laminate is used to form a bag or a box to form a packaging container. Manufacture, after that, using the packaging container, filling and packaging various articles, further, if necessary, boiled or retorted to produce a packaged product, polyamide resin film and Excellent adhesion to deposited films of inorganic oxides such as silicon oxide, excellent transparency, excellent barrier properties to prevent transmission of oxygen, water vapor, etc., and prevention of cracks due to bending and expansion and contraction After that, it is excellent in processability and suppresses the deterioration of barrier properties, and also increases the production line speed to improve the production efficiency, and also improves the water resistance of the polyamide resin film, and fills and packs various articles. , Especially boil or little It is that it is capable of producing a multilayer material using useful transparent barrier film and it is filling and packaging process to. That is, the present invention conventionally forms a vapor-deposited film of an inorganic oxide having a film thickness exceeding 10 nm on one surface of a polyamide-based resin film by a chemical vapor deposition method. First, a plasma processing surface is provided on one side of
Further, a vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the surface of the plasma-treated surface by a chemical vapor deposition method so that the film thickness is in a range of 4 nm to 10 nm. Increasing the production line speed to improve its production efficiency,
In addition, while improving the tight adhesion between the polyamide-based resin film and the inorganic oxide vapor-deposited film, the film quality of the inorganic oxide vapor-deposited film is made flexible, and the occurrence of cracks due to bending and expansion and contraction is prevented. , By reducing the film thickness
Although the oxygen gas barrier property for preventing oxygen gas permeation or the water vapor barrier property for preventing water vapor permeation is slightly reduced, a heat-sealing resin layer is laminated via a primer agent layer or the like. By these, it is possible to improve the oxygen gas barrier property or the water vapor barrier property as well as to enhance the tight adhesion to them, and to cause cracks or the like in the vapor-deposited film of the inorganic oxide in the post-processing steps such as printing and lamination. It is intended to suppress a decrease in barrier properties. Furthermore,
By providing a water-resistant film in advance on one surface of the polyamide resin film, the polyamide resin film prevents swelling and dimensional change due to moisture absorption of water vapor and the like, and silicon oxide by a chemical vapor deposition method. Etc., and can sufficiently form a vapor-deposited film of an inorganic oxide and can withstand boil treatment or retort treatment, and is sufficiently satisfactory in market distribution, storage properties, storage stability, etc. It can produce a packaging product that can be used.

[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 an example of a transparent barrier film according to the present invention.

FIG. 3 is a schematic cross-sectional view schematically showing an example of a layer structure of a laminated material manufactured using the transparent barrier film according to the present invention.

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

FIG. 5 is a schematic cross-sectional view showing an example of a packaging container formed by using the laminated material according to the present invention.

FIG. 6 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

A A ₁ Transparent barrier film B B ₁ Laminate 1 Polyamide resin film 2 Plasma treated surface 3 Inorganic oxide deposited film 4 Water resistant film 5 Primer agent layer 6 Laminate adhesive layer 7 Heat sheet Resin layer 8 anchor coat agent layer 9 seal layer 10 opening

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 77:00 C08L 77:00 F term (Reference) 3E086 AD01 BA04 BA15 BA40 BB02 BB05 BB22 CA01 DA01 4F071 AA54 AG16 AH04 BB08 BC01 BC12 4F100 AA00B AA20B AK46A AK48A AK51G AK63 AR00C AR00D AR00E AT00E BA02 BA03 BA05 BA10B BA10C BA10D BA10E EH66B EJ37A EJ60A EJ61A EJ65E EJ67E GB15 GB23 GB66 JB07C JD01 JD03 JD04 JJ03 JJ07 JK06 JK13 JK14 JK17 JL11E JL12D JL12E JN01 JN01A JN01B YY00B YY00E 4K030 BA44 CA07 CA12 DA02 DA03 JA01 LA01 LA11

Claims (12)

[Claims] 1. A plasma-treated surface is provided on one surface of a polyamide resin film, and a vapor-deposited inorganic oxide film having a thickness of 4 nm to 10 nm is formed on the surface of the plasma-treated surface by a chemical vapor deposition method. A transparent barrier film characterized by being provided. 2. The transparent barrier film according to claim 1, wherein the polyamide-based resin film has a structure in which a water-resistant film is provided in advance on the other surface. 3. The transparent barrier film according to claim 1, wherein the polyamide resin film comprises a biaxially stretched nylon film. 4. The plasma processing surface according to claim 1, wherein the plasma processing surface is a plasma processing surface using an inert gas.
4. The transparent barrier film described in any one of items 1 to 3. 5. The transparent barrier film according to claim 1, wherein the inorganic oxide vapor-deposited film comprises a silicon oxide vapor-deposited film. 6. A plasma-treated surface is provided on one surface of a polyamide resin film, and a vapor-deposited inorganic oxide film having a thickness of 4 nm to 10 nm is formed on the surface of the plasma-treated surface by a chemical vapor deposition method. At least a heat sink is provided on the surface of the deposited inorganic oxide film of the transparent barrier film having the configuration provided through the primer agent layer and the adhesive layer for laminating.
A laminate comprising a sealing resin layer. 7. A plasma-treated surface is provided on one surface of a polyamide resin film, and an inorganic oxide vapor-deposited film having a thickness of 4 nm to 10 nm is formed on the surface of the plasma-treated surface by a chemical vapor deposition method. At least a heat-sealing resin layer is provided on the surface of the vapor-deposited inorganic oxide film of the transparent barrier film having the configuration provided, with a primer agent layer and an anchor coating agent layer interposed therebetween. Laminated material. 8. The laminated material according to claim 6, wherein a base film layer is further laminated on the surface of the polyamide resin film of the transparent barrier film. 9. The method according to claim 6, wherein a base film layer and a heat-sealing resin layer are further laminated on the surface of the polyamide resin film of the transparent barrier film. The laminated material described in. 10. The laminate according to claim 6, wherein the primer agent layer contains a silane coupling agent. 11. The primer agent layer has a thickness of 0.1 g / m.
² to 1.0 g / m ² laminated material described in the above claims 6-10, characterized in that it consists of a range of (dry). 12. The laminated material according to claim 6, wherein the polyamide resin film has a structure in which a water-resistant film is provided in advance on the other surface.