JPH11105189A - Transparent barrier nylon film, and laminated body and container for package using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve transparency, gas barrier properties to oxygen or steam, etc., impact resistance and to provide after-processability by laminating a first thin film and a second thin film with at least two kinds of inorg. oxides on one face of a biaxially drawn nylon film base material. SOLUTION: This transparent barrier nylon film 1 consists of a constitution provided by laminating the first thin film 3 and the second thin film 4 with at least two kinds of inorg. oxides on one face of a biaxially drawn nylon film 2. Practically, as the first thin film 3, a metallized film of an inorg. oxide is provided on one face of the biaxially drawn nylon film 2 by a physical metallizing method and in addition, as the second thin film 4, a metallized film of an inorg. oxide is provided by a plasma chem. deposition method. As the first thin film 3, a thin film prepd. by making an inorg. oxide such as silica amorphous (non-crystalline) is used and as the thin film of silica as the second thin film 4, an org. silicon compd. is used as the raw materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent barrier nylon film, a laminate and a packaging container using the same, and more particularly, to excellent transparency, gas barrier properties against oxygen, water vapor, etc., and impact resistance. Furthermore, it has post-processing suitability such as lamination processing, printing processing, bag making or box making, and prevents the deposition film as a barrier film from peeling off and prevents the occurrence of thermal cracks. It inhibits and prevents its deterioration, and exhibits excellent resistance as a barrier film, and is used for chemicals or cosmetics such as foods and beverages, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, etc. The present invention relates to a transparent barrier nylon film excellent in suitability for packing and preservation of various articles and preservation suitability, and a laminate and a packaging container using the same.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, cosmetics, and others. Such packaging materials vary depending on the purpose of packaging, contents to be filled, storage / distribution of packaged products, etc., but various physical properties are required as packaging materials. Thus, one of these physical properties is a gas barrier property for preventing permeation of oxygen, water vapor, and the like, and this is one of extremely important requirements. Therefore, various types of gas barrier materials for preventing permeation of oxygen and water vapor have been developed and proposed. For example, an aluminum foil, a nylon film or a polyethylene terephthalate film having a coating film of a polyvinylidene chloride resin, a polyvinyl alcohol film, a saponified film of an ethylene-vinyl acetate copolymer, a polyacrylonitrile resin Gas barrier materials such as films have been developed and proposed. Furthermore, in recent years, for example, 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 on a plastic substrate, or a barrier provided with a deposited film of a metal such as aluminum. A conductive film has also been proposed.

[0003]

However, in the above-mentioned aluminum foil, it is difficult to reuse it after use, and when it is incinerated after disposal, incineration ash derived from the metal foil remains, which poses an environmental problem. is there. In the case of a nylon film or a polyethylene terephthalate film having a coating film of the above polyvinylidene chloride resin, if they are discarded after use and incinerated, harmful gases such as chlorine gas are generated. Again, there are environmental issues. Further, in the above-mentioned polyvinyl alcohol film, saponified film of ethylene-vinyl acetate copolymer, polyacrylonitrile resin film, etc., for example, as a content, food is filled, and heat sterilization such as boil treatment or retort treatment is performed. Sometimes, it is difficult to maintain a sufficient barrier property, and there is a problem that the packaged product is affected by temperature, humidity, and the like in the storage and distribution environment. As a solution to the above problems, as described above, in recent years, on a plastic substrate, for example,
Silicon oxide, a transparent barrier film having a configuration provided with a deposited film of an inorganic oxide such as aluminum oxide, or a barrier film having a configuration provided with a deposited film of a metal such as aluminum has been proposed, These materials have little residue even if incinerated after use, and have little deterioration in barrier properties under high humidity, and are widely used as various packaging materials.

[0004] However, 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 the above-mentioned plastic substrate, a plastic substrate such as nylon When a film is used, since the nylon film has an amide group rich in hydrophilicity, it is easily affected by a change in humidity of the external environment, a change in temperature, etc., for example, the nylon film shrinks, and a vapor-deposited film of an inorganic oxide is formed. Even if is formed on a nylon film, it is difficult for the deposited film of the inorganic oxide to follow the change in shrinkage of the nylon film and change, and as a result, the deposited film of the inorganic oxide includes, for example, cracks and the like. And the barrier performance deteriorates with time. Thus, in order to solve such problems, for example, the surface of a nylon film,
For example, various pretreatment methods such as a corona discharge treatment, a plasma treatment, a frame treatment, and a chemical surface treatment have been proposed. However, the adhesion of a deposited inorganic oxide film decreases with time. However, there is a problem that the deposited film is peeled off.
Further, for example, a method of coating a polyester-based, urethane-based, epoxy-based, amine-based, etc. vapor-deposited anchor coating agent and pre-treating the coating agent has been proposed. Insufficient properties, in the vapor deposition process, or in post-processing processes such as lamination or printing, heat damage occurs, cracks and the like are generated in the inorganic oxide vapor deposition film, and the barrier performance is significantly reduced. There is a problem.
Furthermore, a method has been proposed in which a silicon oxide deposited film is formed on a plastic substrate by a plasma chemical vapor deposition method, and an inorganic oxide deposited film is further formed on the deposited film by a physical vapor deposition method. See JP-A-9-123334). This method improves the adhesion and heat resistance between the plastic substrate and the deposited film of the first inorganic oxide, but when a nylon film is used as the plastic substrate, the heat shrinkage of the nylon film is reduced. When the content is 3% or more, cracks occur in the first inorganic oxide deposited film, and further, a plasma chemical vapor deposition method for forming the first inorganic oxide deposited film, particularly,
In the low-temperature plasma chemical vapor deposition method, a highly active plasma is generated in the vapor deposition process, so the plastic substrate itself undergoes a chemical change.Especially in the case of a nylon film, the yellowing is remarkable, and the appearance is colorless. It is extremely difficult to produce a transparent barrier film. Therefore, the present invention uses a nylon film as a plastic substrate, but is excellent in transparency, gas barrier properties against oxygen, water vapor, etc., impact resistance, and the like, and furthermore, laminating, printing, bag making or box making. Has post-processing suitability such as processing, and prevents peeling of the deposited film as a barrier film, and
It prevents the occurrence of thermal cracks, prevents its deterioration and exhibits excellent resistance as a barrier film, and is used for chemicals such as food and drink, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives and adhesives. An object of the present invention is to provide a transparent barrier nylon film excellent in suitability for packing and preservation of various articles such as articles, cosmetics, and others, and a laminate and a packaging container using the same.

[0005]

As a result of various studies to solve the above problems, the present inventor has found that one side of a biaxially stretched nylon film base material is coated with an inorganic oxide by physical vapor deposition. A deposited film is formed, and this is used as a first thin film.
To improve the adhesion of the second thin film formed next to the first thin film and prevent yellowing and deterioration of the biaxially stretched nylon film due to the plasma treatment for forming the second thin film Then, an inorganic oxide deposited film is formed on the first thin film by a plasma enhanced chemical vapor deposition method, and this is used as a second thin film. At least two or more inorganic oxide films are formed. To produce a transparent barrier nylon film by laminating a first thin film and a second thin film according to
A laminate is produced by laminating a polyolefin resin layer having heat sealability or a base film layer on the transparent barrier nylon film, and further using the laminate to form a bag or When the packaging container is manufactured by box making, and various articles are filled and packaged in the packaging container, transparency,
It has excellent gas barrier properties against oxygen, water vapor, etc., impact resistance, etc., and has post-processing suitability such as laminating, printing, bag making or box making. Prevents peeling, and prevents the occurrence of thermal cracks, prevents its degradation and exhibits excellent resistance as a barrier film, food and drink, pharmaceuticals, detergents, shampoos,
Transparent barrier nylon film excellent in filling and packaging suitability and preservation suitability of various articles such as oils, toothpastes, adhesives, adhesives and other chemicals or cosmetics, etc., and laminates and packaging containers using the same. It has been found that the present invention can be produced, and the present invention has been completed.

That is, the present invention is characterized in that a first thin film and a second thin film made of at least two or more inorganic oxides are laminated on one surface of a biaxially stretched nylon film substrate. And a laminate and a packaging container using the same.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of the transparent barrier nylon film according to the present invention, a laminate using the same, and a container for packaging will be described with reference to the drawings by exemplifying a few examples. FIGS. 1 and 2 show the present invention. It is sectional drawing which shows the layer structure of a transparent barrier nylon film, FIG.3, FIG.4, FIG.5 is sectional drawing which shows the layer structure of the laminated body manufactured using the above-mentioned transparent barrier film concerning this invention. 6, FIG. 7, FIG. 8, FIG. 9, and FIG.
FIG. 1 is a plan view or a perspective view showing a configuration of a packaging container made from a bag or a box using a laminate using the transparent barrier nylon film according to the present invention.

As shown in FIG. 1, a transparent barrier nylon film 1 according to the present invention comprises, on one surface of a biaxially stretched nylon film 2, a first thin film 3 made of at least two or more inorganic oxides. It has a configuration in which the second thin film 4 is laminated. Furthermore, specifically, as shown in FIG. 2, the transparent barrier nylon film 1a according to the present invention is provided on one surface of the biaxially stretched nylon film 2,
The first thin film 3 is provided with an inorganic oxide deposited film 3a formed by physical vapor deposition, and the second thin film 4 is further provided with an inorganic oxide deposited film 4a formed by plasma chemical vapor deposition. is there. Thus, the above examples are examples of the transparent barrier nylon film according to the present invention, and are not limited thereto. For example,
Although not shown, the first thin film, the second thin film, and the like may be provided not only on one surface but also on both surfaces of the biaxially stretched nylon film.

Next, a laminate manufactured using the transparent barrier nylon film according to the present invention will be described with reference to a few examples. The laminate according to the present invention is, for example, as shown in FIG. As shown in the figure, a laminate A obtained by laminating at least a polyolefin resin layer 5 having heat sealability on the surface of the second thin film 4 of the transparent barrier nylon film 1 shown in FIG. Can be mentioned. Furthermore, as a laminate according to the present invention, as shown in FIG. 4, at least the base film layer 6 is laminated on the other surface of the biaxially stretched nylon film 2 of the laminate A shown in FIG. The laminated body B can be mentioned.
Alternatively, as the laminate according to the present invention, as shown in FIG. 5, the base film layer 6 of the laminate B shown in FIG.
Can further include a laminate C in which at least a polyolefin-based resin layer 5a having heat sealability is further laminated. Thus, the above-mentioned examples are a few examples constituting the laminate according to the present invention, and are not limited thereto. For example, in the present invention,
Although not shown, in addition to the base film layer, the polyolefin resin layer having heat sealability, etc., depending on the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the application, etc. The substrate can be arbitrarily laminated and various types of laminates can be designed and manufactured. In the present invention, the base film layer, the polyolefin-based resin layer having heat sealability, and the other layers may be arbitrarily laminated according to the purpose of use, application, and the like. Can be designed and manufactured.

Next, in the present invention, the structure of the packaging container according to the present invention, which is made from a bag or a box using the above-described laminate, will be described. By way of example, a description will be given of a packaging container made from a bag or a box using the laminated material A shown in FIG. 3. As shown in a perspective view of FIG. 6, two laminated bodies A and A are prepared. Then, the surfaces of the polyolefin-based resin layers 5 and 5 having heat sealability, which are located in the innermost layer, are superposed on each other, and thereafter, the three edges of the outer periphery are sealed.
By forming the seal portions 7, 7, 7 by sealing, the three-way seal type flexible packaging container D according to the present invention can be manufactured.

Next, as the packaging container according to the present invention, as shown in the plan view of FIG.
First, a predetermined crease l is used.
(Shown by a dotted line), a blank plate 9 for forming a paper container having a sticking portion 8 or the like is manufactured by punching, and then, as shown in a perspective view of FIG. The attachment portion 8 is overlapped with the other side end portion 10 (shown in FIG. 7), and the overlapped portion is heat-sealed to form a side end seal portion 11 to produce a body portion 12, and further, The lower portion of the body 12 is folded in a conventional manner to form a heat seal to form a bottom portion 13, and the upper portion thereof is heat-sealed in a conventional manner.
Then, the roof type sealing portion 14 is formed to manufacture the roof type paper packaging container E according to the present invention.

Further, as a packaging container according to the present invention, as shown in the plan view of FIG.
First, a blank material 9a for forming a rectangular paper container having a sticking portion 8a and the like, which is capable of forming a cylindrical body portion, is punched out from the laminate material C, and then manufactured. FIG.
As shown in the perspective view of FIG.
a is overlapped with the other side end 10a (shown in FIG. 9),
The overlapped portion is heat-sealed to form a side end seal portion 11a to produce a cylindrical body portion 12a.
In the lower portion of 2a, for example, a bottom plate 15 is formed by heat sealing a cylindrical bottom plate 15 to form a bottom seal portion 16, and further in the upper portion of the cylindrical container 12a, for example. ,
Heat sealing a cylindrical lid plate 19 having a drinking opening 18 sealed with a peeling off piece 17 to form an upper seal portion 20
Is formed to form the lid 19a, and the cylindrical paper can-shaped packaging container F according to the present invention can be manufactured. In the present invention, it is needless to say that the present invention is not limited to the above-illustrated packaging container, and that various types of packaging containers can be manufactured depending on the purpose, application, and the like. Needless to say.

Next, in the present invention, the materials constituting the transparent barrier nylon film, the laminate, the packaging container and the like according to the present invention as described above, and the manufacturing method thereof will be described. Can employ various ones. First, in the present invention, the material constituting the transparent barrier nylon film according to the present invention will be described. First, as the biaxially stretched nylon film, a nylon film capable of holding a first thin film and a second thin film is also used. Any material can be used as long as the film or sheet is made of nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, or various other polyamide-based resins. it can. The film or sheet of these resins is preferably stretched biaxially, and has a thickness of 10 to 50 μm.
And preferably about 10 to 25 μm. Also,
If necessary, a film or sheet of the above resin may be provided on its surface, for example, by corona treatment, plasma treatment,
A surface treatment such as a framing treatment or the like can be optionally performed. Further, in the present invention, in order to achieve strong adhesion to the first thin film, for example, a polyester-based, urethane-based, epoxy-based, amine-based or other anchor coating agent is used for the first thin film. In the deposition process to form a thin film,
It can be formed in-line or off-line. Furthermore, in the present invention, depending on the application, for example, an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, and other additives as desired, within a range that does not affect the transparency thereof. In addition, a nylon film or the like containing them can also be used.

Next, in the present invention, as the first thin film constituting the transparent barrier nylon film, any thin film obtained by converting an inorganic oxide into amorphous (amorphous) can be basically used. For example, an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, potassium oxide, tin oxide, sodium oxide, boron oxide, titanium oxide, lead oxide, zirconium oxide, and yttrium oxide is made amorphous. A thin film can be used. In the present invention, as the first thin film, specifically, for example, an inorganic oxide made of the above metal oxide or a metal is used, and if necessary, an oxygen gas or the like is supplied. Meanwhile, physical vapor deposition methods such as a vacuum vapor deposition method, a sputtering method, and an ion plating method (physical vapor deposition method, Physical Vap
or Deposition method, PVD method)
A deposited film of an inorganic oxide is formed and can be used as a first thin film. In the above, for example, an electron beam (EB) method, a high-frequency induction heating method, a resistance heating method, or the like is used as a method for heating the deposition material. The above-mentioned physical vapor deposition method will be described more specifically by taking an example of a roll-up type vacuum vapor deposition machine as an example. As shown in a schematic configuration diagram of FIG. A biaxially stretched nylon film 114 unwound from an unwinding roll 113
Is applied to the deposition chamber -1 via the coating drum 115.
16, where the metal or metal oxide heated as the evaporation source in the crucible 117 is evaporated, and at this time, the cooled core is blown out while oxygen gas or the like is ejected from the oxygen outlet 118. Masks 119 and 11 on the biaxially stretched nylon film 114 of the
9, a biaxially stretched nylon film 114 having the deposited film formed thereon is fed into a vacuum chamber 112 and taken up by a take-up roll 120, thereby forming a first roll. It is possible to produce an inorganic oxide vapor-deposited film by a physical vapor deposition method as a thin film.

In the present invention, when a deposited film of an inorganic oxide is formed on a biaxially stretched nylon film by a plasma chemical vapor deposition method, the surface of the biaxially stretched nylon film is affected by plasma treatment, and It is extremely difficult to improve the yellowing, deterioration, and the like. Therefore, it is very difficult to improve the yellowing, deterioration, and the like. An inorganic oxide vapor-deposited film is formed as a thin film by a physical vapor deposition method, and this is used as a plasma-resistant protective layer against plasma treatment by a plasma chemical vapor deposition method. Further, in the present invention, the deposited film of the inorganic oxide by the physical vapor deposition method as the first thin film improves the adhesion of the second thin film to the first thin film. That is, by forming the first thin film with an inorganic oxide vapor-deposited film, the affinity with the inorganic oxide vapor-deposited film formed by the plasma chemical vapor deposition method as the second thin film is improved, and the adhesion strength is increased. It is. In the present invention, in order to further improve the above-mentioned adhesion strength, by holding a biaxially stretched nylon film having a vapor deposited film of an inorganic oxide as a first thin film in the atmosphere for a long time, or in-line or It is also possible to introduce hydroxyl groups on the surface of the inorganic oxide vapor deposition film as the first thin film by oxygen plasma treatment offline. For example, the first
When the inorganic oxide deposited film as a thin film of aluminum is an aluminum oxide deposited film, oxygen (aluminum oxide) directly connected to aluminum and a hydroxyl group (aluminum hydroxide)
It is preferable that the weight ratio be 40:60 to 70:30. Thus, in the present invention, the above-mentioned plasma-resistant protective layer, and further, the first thin film for improving the adhesion of the second thin film, are excellent in transparency and are made of amorphous inorganic oxide. A vapor-deposited film is preferred, and specifically,
A deposited film of aluminum oxide or magnesium oxide is preferable. Further, in the present invention, the thickness of the first thin film is preferably about 100 to 300 °, more preferably about 150 to 250 °. It is not preferable because cracks and the like easily occur in the film,
On the other hand, if the angle is less than 150 ° or even less than 100 °, it is difficult to achieve the effect, which is not preferable.

Next, in the present invention, the second thin film constituting the transparent barrier nylon film can be basically used as long as it is a thin film in which an inorganic oxide is made amorphous (amorphous). For example, an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, potassium oxide, tin oxide, sodium oxide, boron oxide, titanium oxide, lead oxide, zirconium oxide, and yttrium oxide is made amorphous. A thin film can be used. In the present invention, as the first thin film, specifically, for example, an inorganic oxide composed of a metal oxide as described above, or a metal, an organic silicon compound, or the like is used as a raw material. While supplying oxygen gas and the like, a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method (plasma chemical vapor deposition method, Chemical Vapor Depth)
A deposition film of an inorganic oxide is formed by an oxidation method, an oxidation method, or the like, and can be used as the second thin film. In the present invention, the thickness of the second thin film as described above is about 50 to 300 °, more preferably,
It is preferable that the thickness is about 100 to 250 °. In the above, if the thickness is more than 300 ° or more than 250 °, cracks or the like are easily generated in the film, which is not preferable, and if it is less than 100 ° or even less than 50 °. However, it is not preferable because it is difficult to exhibit the barrier effect.

In the present invention, as the second thin film, it is desirable to use a continuous layer mainly composed of silicon oxide and SiO _x (X is a number from 0 to 2). From the viewpoints of transparency, barrier properties, etc., SiO _x (X
Represents a number of 1.7 to 2.0). Furthermore, the thin film mainly composed of silicon oxide as the second thin film is made of a silicon compound having at least silicon and oxygen as constituent elements, and further contains one or more elements of carbon or hydrogen as trace constituent elements. And the film thickness is 100 to 300
It is preferably within the range of Å. Thus,
In the present invention, as the silicon oxide thin film as the second thin film as described above, an organic silicon compound as a raw material, a vapor-deposited film formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like. Can be used. In the above description, examples of the organic silicon compound include:
1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, Vinyl trimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the above organosilicon compounds,
1.1.3.3-tetramethyldisiloxane or
The use of hexamethyldisiloxane as a raw material, due to its handleability, the characteristics of the formed deposited film, etc.
In particular, it is a preferred raw material. In the above, as the low-temperature plasma generator, for example, high-frequency plasma,
It is possible to use a generator such as a pulsed plasma or a microwave plasma. In the present invention, in order to obtain a highly active and stable plasma, it is necessary to use a generator based on a high-frequency plasma method. desirable. The above-mentioned plasma chemical vapor deposition method will be described in more detail with reference to an example. As shown in a schematic configuration diagram of FIG. 12, a vacuum chamber 21 of a plasma chemical vapor deposition apparatus 211
A biaxially stretched nylon film 214 on which a first thin film is unwound from an unwinding roll 213 disposed inside
Is conveyed at a constant speed via an auxiliary roll 215, and on the peripheral surface of the cooling / electrode drum 216,
A mixed gas composed of an organic silicon compound, oxygen gas, inert gas, or the like, supplied from the raw material volatilizing and supplying devices 217, 218, and 219 is introduced through the raw material supply nozzle 220, and the glow
By the discharge plasma 221, a deposited film of silicon oxide is formed.
The film is formed on the first thin film of the biaxially stretched nylon film 214 and formed into a film.
Is a power supply 22 arranged outside the vacuum chamber-212.
2, a predetermined voltage is applied, and a magnet 223 is arranged near the cooling / electrode drum 216 to promote the generation of plasma. The axially stretched nylon film 214 can be wound on a winding roll 224 via an auxiliary roll 215 to produce the transparent barrier nylon film according to the present invention. In the drawing, reference numeral 225 denotes a vacuum pump.

As described above, the transparent barrier nylon film according to the present invention comprises a first thin film and a second thin film of at least two or more inorganic oxides on one surface of a biaxially stretched nylon film substrate. Thus, the first thin film is composed of an inorganic oxide vapor-deposited film by physical vapor deposition, and the second thin film is composed of an inorganic oxide vapor-deposited film by plasma chemical vapor deposition. This makes it possible to produce a nylon film having high barrier properties and excellent transparency and adhesion to a substrate. That is, in the transparent barrier nylon film according to the present invention, the inorganic thin film deposited by physical vapor deposition as the first thin film is non-crystalline. Cracks and the like do not occur even with a change due to, for example, the function of protecting the inorganic oxide deposited film by the plasma enhanced chemical vapor deposition method as the second thin film as the barrier layer. Without impairing the functions such as the barrier properties of the inorganic oxide deposited film by the plasma enhanced chemical vapor deposition method, this makes it possible to produce a transparent barrier nylon film having excellent transparency and further having an extremely high barrier property. It is. Incidentally, the transparent barrier nylon film according to the present invention has an oxygen permeability of 2
cc / m ² / day (23 ° C./90% RH) or less.

Next, in the present invention, the innermost layer of the laminate,
Alternatively, as the polyolefin-based resin constituting the heat-sealing polyolefin-based resin layer forming the outermost layer, a resin film or sheet which can be melted and fused to each other by heat can be used. ,In particular,
For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer,
Ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, Acid-modified polyolefin resin obtained by modifying polyolefin resin such as polybutene polymer, polyethylene or polypropylene with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate Films or sheets of various resins such as a resin, a poly (meth) acrylic resin, a polyvinyl chloride resin and others can be used. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film, film or sheet is preferably about 5 μm to 300 μm, and more preferably about 10 μm to 100 μm.

Next, in the present invention, the base film constituting the base film layer forming the laminate includes:
For example, when constituting a packaging container, since it is a basic material, it has excellent properties in mechanical, physical, chemical, etc., especially, it has strength, toughness, and heat resistance Can be used, specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin And a film or sheet of a tough resin such as polyacetal resin, fluorine resin and others. 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.
The order of μm to 50 μm is desirable. In the present invention, for example, characters,
A desired printed pattern such as a figure, a symbol, a picture, or a pattern may be subjected to front printing or back printing by a normal printing method.

Next, in the present invention, as the base film constituting the base film layer, for example, various paper base materials constituting the paper layer can be used. In the present invention, the paper substrate is provided with moldability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper substrate, or pure white roll paper,
Paper base materials such as kraft paper, paperboard, and 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 Density polyethylene, polypropylene, film or sheet of resin such as ethylene-propylene copolymer, or, oxygen, polyvinylidene chloride having a barrier property against water vapor, etc.,
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, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, 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 can be used in 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 of manufacturing a laminate using the above-mentioned materials in the present invention will be described. As the method, a conventional packaging material is laminated.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pre-treatment such as a corona treatment, an ozone treatment, a framing treatment, or the like can be performed on the film. Anchor coating agents such as polyester, isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate And known adhesives such as adhesives for laminates such as cellulose, cellulose, etc.
Coating agents, adhesives and the like can be used.

Next, in the present invention, a method for producing a bag or a box using the above-mentioned laminate will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using the laminated body manufactured by such a method, the heat-sealing resin layer of the inner layer is opposed to the laminated body, and the heat-sealing resin layer is folded, or the two sheets are overlapped, and the peripheral end portion is further folded. A bag can be formed by providing a seal portion by heat sealing. Thus, as a bag making method, the above-mentioned laminate is folded with its inner layer facing the surface, or two of them are overlapped,
Further, the peripheral end portion of the outer periphery is formed, for example, by a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket-attached seal type ( According to the present invention, a heat seal is formed according to a heat seal form such as a (pyrro-seale type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. Various forms of packaging containers can be manufactured. Others, for example, self-supporting packaging bags (standing pouches)
And the like can be manufactured, and in the present invention, a tube container and the like can be manufactured using the above-mentioned laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal,
Can be performed by a known method such as In the present invention, a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

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

In the present invention, the packaging container produced as described above is excellent in transparency, gas barrier properties against oxygen, water vapor, etc., impact resistance, and the like.
Having post-processing suitability such as printing, bag making or box making,
Further, it prevents peeling of the vapor-deposited thin film as a barrier film, and prevents the occurrence of thermal cracks, prevents its deterioration, and exhibits excellent resistance as a barrier film, for example, It has excellent suitability for filling and packaging, preservation, etc. of various articles such as chemicals and cosmetics such as medicines, detergents, shampoos, oils, toothpastes, adhesives and adhesives, and others.

[0028]

【Example】

Example 1 (1). A biaxially stretched nylon film having a thickness of 15 μm was used as a substrate, and was used as an electron beam (EB).
The protective film was attached to a delivery roll of a heating type PVD vacuum evaporation machine, and a protective layer composed of an aluminum oxide evaporation film was formed on the corona-treated surface of the nylon film under the following conditions. Deposition material: aluminum Degree of vacuum in vacuum chamber: 2.5 × 10 ⁻³ mbar Degree of vacuum in deposition chamber before oxygen introduction: 2.2 × 10
^-4 mbar Degree of vacuum in the deposition chamber after introducing oxygen: 3.1 × 10
^-4 mbar Film transport speed: 580 m / min EBpower: 0.8 A Evaporation surface: Corona treated surface Oxygen plasma treatment: Available (oxygen introduction amount = 150 mL / m
in) Thickness of deposited film: 190 ° (X-ray fluorescence analysis) (2). The biaxially stretched nylon film having the aluminum oxide vapor-deposited film produced above was subjected to a high-frequency plasma method C
A barrier layer composed of a silicon oxide vapor-deposited film was formed on a delivery roll of a VD vapor deposition device under the following conditions on a biaxially stretched nylon film aluminum oxide vapor-deposited film. A barrier nylon film was manufactured. Reaction gas mixture ratio: 1.1.3.3-tetramethyldisiloxane: oxygen gas: helium = 1: 10: 8 Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Vacuum in vapor deposition chamber Degree: 3.8 × 10 ^-2 mbar Cooling / electrode drum supply power: 10 kW Film transfer speed: 120 m / min Thickness of deposited film: 140 ° (X-ray fluorescence analysis) (3). The transparent barrier nylon film according to the present invention produced above has a thickness of 50
A low-density polyethylene film having a thickness of μm was laminated by a dry lamination method to produce a laminate according to the present invention having the following layer constitution. In the above, a two-component curable urethane-based adhesive is used as the adhesive, and the amount of the adhesive is 4.5 g / m 2.
² (solid content). 15 μm thick biaxially stretched nylon film / aluminum oxide deposited film / silicon oxide deposited film / adhesive layer / 50 μm thick low density polyethylene film

Embodiment 2 (1). A biaxially stretched nylon film having a thickness of 15 μm was used as a substrate, and was used as an electron beam (EB).
It was mounted on a delivery roll of a heating type PVD vacuum vapor deposition machine, and a protective layer composed of a magnesium oxide vapor deposition film was formed on the corona-treated surface of the above nylon film under the following conditions. Vapor deposition material: magnesium Vacuum degree in vacuum chamber: 3.0 × 10 ⁻³ mbar Vacuum degree in vapor deposition chamber before oxygen introduction: 2.5 × 10
^-4 mbar Degree of vacuum in the deposition chamber after introducing oxygen: 3.0 × 10
^-4 mbar Film transport speed: 500 m / min EBpower: 0.6 A Evaporation surface: Corona treated surface Oxygen plasma treatment: Available (oxygen introduction amount = 450 mL / m
in) Thickness of deposited film: 220 ° (X-ray fluorescence analysis) (2). The biaxially stretched nylon film having a magnesium oxide vapor-deposited film produced as described above was subjected to high frequency plasma method C
A barrier layer composed of a silicon oxide vapor-deposited film was formed on a magnesium oxide vapor-deposited film of a biaxially stretched nylon film under the following conditions. A barrier nylon film was manufactured. Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 8 Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar Degree of vacuum in vapor deposition chamber: 4.0 × 10 ^{− 2} mbar Cooling / electrode drum supply power: 10 kW Film transport speed: 140 m / min Thickness of deposited film: 100 ° (X-ray fluorescence analysis) (3). The transparent barrier nylon film according to the present invention produced above has a thickness of 50
A low-density polyethylene film having a thickness of μm was laminated by a dry lamination method to produce a laminate according to the present invention having the following layer constitution. In the above, a two-component curable urethane-based adhesive is used as the adhesive, and the amount of the adhesive is 4.5 g / m 2.
² (solid content). 15 μm thick biaxially stretched nylon film / magnesium oxide vapor deposited film / silicon oxide vapor deposited film / adhesive layer / 50 μm thick low density polyethylene film

Embodiment 3 (1). A biaxially stretched nylon film having a thickness of 15 μm was used as a base material, and a two-component curable deposition anchor coating agent (main agent: nitrified cotton / polyester polyol system, Curing agent: isocyanate
Biaxially stretched nylon coated with a coating amount of 0.3 g / m ² (dry) by a gravure coating method, and then coated with the above-mentioned deposited anchor coating agent. Electron beam (EB) heating type PV film
D: The film was mounted on a delivery roll of a vacuum vapor deposition machine, and a protective layer composed of a vapor-deposited aluminum oxide film was formed on the vapor-deposited anchor coat surface of the nylon film under the following conditions. Deposition material: aluminum Degree of vacuum in vacuum chamber: 2.5 × 10 ⁻³ mbar Degree of vacuum in deposition chamber before oxygen introduction: 2.2 × 10
^-4 mbar Degree of vacuum in the deposition chamber after introducing oxygen: 3.1 × 10
^-4 mbar Film transport speed: 550 m / min EBpower: 0.8 A Evaporation surface: Anchor coating treatment surface Oxygen plasma treatment: None Thickness of evaporation film: 210 ° (X-ray fluorescence analysis method) (2). The biaxially stretched nylon film having the aluminum oxide vapor-deposited film produced as described above is kept under a constant temperature and humidity condition of 40 ° C./90% RH for 2 days, and then mounted on a delivery roll of a high frequency plasma type CVD vapor deposition apparatus. Under the following conditions, a barrier layer composed of a silicon oxide vapor-deposited film was formed on the aluminum oxide vapor-deposited film of the biaxially stretched nylon film to produce a transparent barrier nylon film according to the present invention. Reaction gas mixing ratio: 1.1.3.3-tetramethyldisiloxane: oxygen gas: helium = 1: 11: 6 Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar Vacuum in vapor deposition chamber Degree: 3.8 × 10 ^-2 mbar Cooling / electrode drum supply power: 10 kW Film transport speed: 105 m / min Thickness of deposited film: 160 ° (X-ray fluorescence analysis) (3). The transparent barrier nylon film according to the present invention produced above has a thickness of 50
A low-density polyethylene film having a thickness of μm was laminated by a dry lamination method to produce a laminate according to the present invention having the following layer constitution. In the above, a two-component curable urethane-based adhesive is used as the adhesive, and the amount of the adhesive is 4.5 g / m 2.
² (solid content). 15 μm thick biaxially stretched nylon film / aluminum oxide deposited film / silicon oxide deposited film / adhesive layer / 50 μm thick low density polyethylene film

Example 4 In Example 1, except that the deposition rate of aluminum oxide was 430 m / min and the film thickness was 250 °,
A transparent barrier nylon film according to the present invention was produced in exactly the same conditions as in Example 1 above. Next, a two-part curable urethane-based anchor coating agent was coated on the surface of the silicon oxide vapor-deposited film of the transparent barrier nylon film according to the present invention produced as described above, with a coat amount of 0.2 g / g.
m ² (solid content) and coat with anchor
A coating agent layer, and then on the anchor coating agent layer surface,
40 μm thick linear low-density polyethylene film (L-
LDPE) was laminated with a melt-extruded low-density polyethylene layer having a thickness of 15 μm by an extrusion lamination method to produce a laminate according to the present invention having the following layer constitution.
15 μm thick biaxially stretched nylon film / aluminum oxide deposited film / silicon oxide deposited film / anchor coating agent layer / 15 μm thick low density polyethylene layer / 40 thickness
μm linear low density polyethylene film

Example 5 In Example 2 described above, except that the deposition rate of magnesium oxide was 580 m / min and the film thickness was 190 °,
A magnesium oxide vapor-deposited film was formed in exactly the same manner as in Example 2 above, and then the silicon oxide vapor-deposited film was formed on the magnesium oxide-deposited film surface in exactly the same manner as in Example 1 above. Was formed to produce a transparent barrier nylon film according to the present invention. Next, a two-component curable urethane-based adhesive was coated on the surface of the silicon oxide vapor-deposited film of the transparent barrier nylon film according to the present invention produced above at a coat weight of 5.0 g / m ² (solids). Amount)
To form an adhesive layer. Then, an ethylene-α-olefin copolymer film (metallocene polyethylene, MP) having a thickness of 40 μm is formed on the surface of the adhesive layer.
E) was laminated with a melt-extruded low-density polyethylene layer having a thickness of 20 μm by extrusion lamination to produce a laminate according to the present invention having the following layer constitution. Thickness 1
5 μm biaxially stretched nylon film / deposited film of magnesium oxide / deposited film of silicon oxide / adhesive layer / 20 μm thick
m low density polyethylene layer / 40 μm thick ethylene
α-olefin copolymer film

Comparative Example 1 A biaxially stretched nylon film having a thickness of 15 μm was used as a substrate, and the corona-treated surface thereof was formed by the same method using the plasma chemical vapor deposition method described in (2) of Example 1 above. In the same manner under the same conditions, a deposited silicon oxide film was formed to produce a transparent barrier nylon film. Next, a low-density polyethylene film having a thickness of 50 μm is laminated on the surface of the vapor-deposited silicon oxide film of the transparent barrier nylon film produced above by a dry lamination method to produce a laminate having the following layer constitution. did. In the above, a two-component curable urethane-based adhesive was used as the adhesive, and the amount of the adhesive was 4.5 g / m ² (solid content). Thickness 1
5 μm biaxially stretched nylon film / silicon oxide deposited film / adhesive layer / 50 μm thick low density polyethylene film

Comparative Example 2 The same conditions were applied to the surface of the silicon oxide deposited film of the transparent barrier nylon film produced in Comparative Example 1 by using the physical vapor deposition method described in (1) of Example 1 above. In the same manner, a deposited film of aluminum oxide was formed to produce a transparent barrier nylon film. Next, a low-density polyethylene film having a thickness of 50 μm is laminated on the surface of the aluminum oxide vapor-deposited film of the transparent barrier nylon film produced above by a dry lamination method to produce a laminate having the following layer constitution. did. In the above, a two-component curable urethane-based adhesive was used as the adhesive, and the amount of the adhesive was 4.5 g / m ² (solid content). 15 μm thick biaxially stretched nylon film / silicon oxide deposited film / aluminum oxide deposited film / adhesive layer / thickness 50
μm low density polyethylene film

Comparative Example 3 In Comparative Example 2 described above, instead of forming a vapor-deposited film of aluminum oxide on the surface of the vapor-deposited silicon oxide film of the transparent barrier nylon film, a description was made in (1) of Example 1 above. A magnesium oxide deposited film was formed in the same manner using the physical vapor deposition method under the same conditions to produce a transparent barrier nylon film. Next, a low-density polyethylene film having a thickness of 50 μm was laminated on the surface of the magnesium oxide vapor-deposited film of the transparent barrier nylon film produced above by a dry lamination method to produce a laminate having the following layer constitution. did. In the above, a two-component curable urethane-based adhesive is used as the adhesive, and the amount of the adhesive is:
It was 4.5 g / m ² (solid content). 15 μm thick biaxially stretched nylon film / silicon oxide deposited film / magnesium oxide deposited film / adhesive layer / 50 μm thick low density polyethylene film

Comparative Example 4 A laminated body having the following layer structure was produced in the same manner as in Example 1 except that the thickness of the deposited aluminum oxide film was changed to 350 °. Thickness 15
μm biaxially stretched nylon film / aluminum oxide deposited film / silicon oxide deposited film / adhesive layer / 50 μm thick
Low density polyethylene film

Comparative Example 5 The same procedure as in Example 1 was carried out except that the thickness of the deposited silicon oxide film formed on the deposited aluminum oxide film was 320 °. A laminate having a layer configuration was manufactured. 15 μm thick biaxially stretched nylon film / aluminum oxide deposited film / silicon oxide deposited film / adhesive layer / 50 μm thick low density polyethylene film

EXPERIMENTAL EXAMPLE 1 The transparent barrier nylon films produced in Examples 1 to 5 and Comparative Examples 1 to 5 were prepared as follows.
Was measured. (1). Measurement of Constituent Element Ratio in Inorganic Oxide Vapor Deposition Film by Plasma Chemical Vapor Deposition Method This was measured with a measuring device [model name, ESCA (ESCA)] manufactured by VG Scientific, USA. (2). Measurement of film thickness of first thin film and second thin film This was measured by X-ray fluorescence analysis. (3). 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. (4). Measurement of color This was visually observed by coloring. The above measurement results are shown in Table 1 below.

[0039]

[Table 1] In the above description, the oxygen permeability was measured after forming the first thin film and after forming the second thin film.

As is clear from the above results, Example 1
-5 were all good. Note that the effect of suppressing yellowing could be confirmed only when the first thin film was formed by physical vapor deposition. In addition, it was confirmed that when the first thin film was formed by the plasma chemical vapor deposition method, the barrier property was not finally improved. Furthermore, the first
It was confirmed that when both the thin film and the second thin film were thick, the barrier property was not improved finally. This is presumed to be due to mechanical cracks occurring during the deposition process when the thickness of the deposited film is large because the first thin film and the second thin film are formed discontinuously.

EXPERIMENTAL EXAMPLE 2 Next, using the transparent barrier nylon films produced in Examples 1 to 5 and Comparative Examples 1 to 5, a laminate produced therefrom was first subjected to 15 cm × 15 cm.
A flat pouch having a size was prepared, and then filled with 50 ml of distilled water through the opening, and then the opening was heat-sealed to produce a packaged product. Next, the packaged product produced above was kept in boiling water for 10 minutes, and then the water was taken out and the oxygen permeability was measured. This is the temperature 23
C., humidity 90% RH, USA, MOCON (MOCO
N) [Model name, OXTRA
N)]. The results are shown in Table 2 below.

[0042]

[Table 2]

As is clear from the above results, in Examples 1 to 5 above, no decrease in oxygen barrier properties was observed even after the boiling treatment, and all were 5 cc / m ² or less. . On the other hand, in all of Comparative Examples 1 to 5, the oxygen barrier properties were significantly reduced by the boiling treatment. This is presumed to be due to the fact that due to the boiling treatment, the adhesion between the base material and the deposited film of the inorganic oxide deteriorates, and as a result, the oxygen barrier property deteriorates.

Example 6 Using the laminate produced in Example 1 above, a three-way seal-type plastic bag was produced by a bag making machine.
Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled and packaged product. However, no deterioration of the barrier properties was observed, and extremely good results were obtained.

Example 7 A low-density polyethylene was used on the biaxially stretched nylon film surface of the laminate produced in Example 1 above, and this was extruded to a thickness of 100 μm and laminated. Laminated material was manufactured. Low-density polyethylene layer having a thickness of 100 μm / biaxially oriented nylon film having a thickness of 15 μm / a deposited film of aluminum oxide / a deposited film of silicon oxide / adhesive layer / low-density polyethylene film having a thickness of 50 μm First, the laminated material is rolled and the overlapped edge is heat-welded to produce a tubular body for forming a tube. Next, polypropylene is attached to one end of the tubular body. A neck was formed by injection molding using a resin, and a cap was screwed onto the neck to produce a tube container. Next, the contents were filled from the other opening of the above tube container, and then the opening was heat-sealed to produce a tube-shaped packaged product. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

Example 8 A low-density polyethylene was used on the surface of the biaxially stretched nylon film of the laminate manufactured in Example 2 to a thickness of 30%.
While extruding at μm, a paper having a basis weight of 200 g / m ² is extruded by sand laminating, and a high pressure method low density polyethylene is extruded to a thickness of 30 μm on the surface of the paper.
Then, a laminated material having the following configuration was manufactured. Thickness 3
0 μm low-density polyethylene layer / 200 g / m ² basis weight paper layer / 30 μm-thick low-density polyethylene layer / thickness 15
μm biaxially stretched nylon film / magnesium oxide vapor deposition film / silicon oxide vapor deposition film / adhesive layer / thickness 50 μm
Using the laminated material produced above, first, a blank plate for forming a paper container is manufactured from the laminated material, and the polymerized edge portion is thermally welded using the blank plate to form a paper container. Was manufactured, and then one bottom of the square body was folded and sealed to form a bottom, thereby manufacturing a paper container. Next, the contents are filled from the opening above the paper container, and then the opening is heat-sealed to form a roof-type upper seal, thereby producing a packaged product. did. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

[0047]

As is apparent from the above description, the present invention forms an inorganic oxide vapor-deposited film by physical vapor deposition on one surface of a biaxially stretched nylon film base material,
And a biaxially stretched nylon film formed by plasma treatment for improving the adhesion of the second thin film to be formed next to the first thin film and forming the second thin film. A plasma-resistant protective layer for preventing yellowing and deterioration, and then, on the first thin film, an inorganic oxide vapor-deposited film is formed by a plasma-enhanced chemical vapor deposition method. A first thin film and a second thin film of two or more inorganic oxides are laminated to produce a transparent barrier nylon film, and the transparent barrier nylon film further comprises a heat-sealing polyolefin. Resin layer,
Alternatively, a laminate is produced by laminating a base film layer or the like, and further, a bag is made or box-formed using the laminate to produce a packaging container, and various articles are placed in the packaging container. Filled and packed, it has excellent transparency, gas barrier properties against oxygen, water vapor, etc., impact resistance, etc., and has post-processing suitability such as laminating, printing, bag making or box making.
Prevent peeling of the deposited thin film as a barrier film, and prevent the occurrence of thermal cracks, prevent its deterioration,
Exhibits excellent resistance as a barrier film, and is suitable for filling and packaging of various products such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other chemicals or cosmetics, and others. In addition, a transparent barrier nylon film having excellent storage suitability and the like, and a laminate and a packaging container using the same can be produced.

[Brief description of the drawings]

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

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

FIG. 3 is a cross-sectional view showing a layer structure of a laminate manufactured using the transparent barrier nylon film according to the present invention.

FIG. 4 is a cross-sectional view showing a layer structure of a laminate manufactured using the transparent barrier nylon film according to the present invention.

FIG. 5 is a cross-sectional view showing a layer structure of a laminate manufactured using the transparent barrier nylon film according to the present invention.

FIG. 6 is a perspective view showing a configuration of a packaging container made from a bag or a box using a laminate using the transparent barrier nylon film according to the present invention.

FIG. 7 is a plan view showing the configuration of a packaging container made from a bag or a box using a laminate using the transparent barrier nylon film according to the present invention.

FIG. 8 is a perspective view showing a configuration of a packaging container made from a bag or a box using a laminate using the transparent barrier nylon film according to the present invention.

FIG. 9 is a plan view showing a configuration of a packaging container formed from a bag or a box using a laminate using the transparent barrier nylon film according to the present invention.

FIG. 10 is a perspective view showing a configuration of a packaging container made from a bag or a box using a laminate using the transparent barrier nylon film according to the present invention.

FIG. 11 is a configuration diagram showing a schematic configuration of a take-up type vacuum evaporation machine.

FIG. 12 is a configuration diagram showing a schematic configuration of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent barrier nylon film 1a Transparent barrier nylon film 2 Biaxially stretched nylon film 3 First thin film 3a Deposited film of inorganic oxide 4 Second thin film 4a Deposited film of inorganic oxide 5 Heat sealability Polyolefin-based resin layer 5a Polyolefin-based resin layer having heat-sealing property 6 Base film layer 7 Seal portion 8 Adhering portion 9 Blank plate for forming paper container 10 Side end 11 Side end seal Part 12 Body part 13 Bottom part 14 Roof type seal part 8a Sticking part 9a Blank plate for forming paper container 10a Side end part 11a Side end seal part 12a Cylindrical body part 15 Cylindrical bottom plate 15a Bottom part 16 Bottom Seal part 17 Peeling piece 18 Drinking port 19 Cylindrical lid plate 19a Lid part 20 Upper seal part A Laminate B Laminate C Laminate D Three-way seal type flexible packaging container E Roof Container l Orikei for for paper packaging container F cylindrical paper cans like packaging

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C23C 28/04 C23C 28/04 // C08J 7/00 306 C08J 7/00 306 7/04 CFG 7/04 CFGP

Claims (13)

[Claims] 1. A transparent barrier comprising a first film and a second film made of at least two kinds of inorganic oxides laminated on one surface of a biaxially stretched nylon film substrate. Nylon film. 2. The transparent barrier nylon film according to claim 1, wherein the first thin film is a deposited film of an inorganic oxide formed by a physical vapor deposition method. 3. The transparent barrier nylon film according to claim 1, wherein the second thin film is an inorganic oxide vapor-deposited film formed by a plasma chemical vapor deposition method. 4. The first thin film improves the adhesion of the second thin film to the first thin film, and the yellowing and deterioration of the biaxially stretched nylon film due to the plasma treatment for forming the second thin film. 4. The transparent barrier nylon film according to claim 1, wherein the transparent barrier nylon film is a plasma-resistant protective layer for preventing the formation of a film. 5. The method according to claim 1, wherein the first thin film is made of a non-crystalline aluminum oxide or magnesium oxide thin film, and has a thickness in the range of 100 to 300 °. 5. The transparent barrier nylon film described in 2, 3, or 4. 6. The second thin film is a thin film provided on a plasma processing surface of the first thin film, and the thin film is made of a silicon compound having at least silicon and oxygen as constituent elements. As a trace constituent element, one or more elements of carbon or hydrogen are contained.
The transparent barrier nylon film according to any one of claims 1, 2, 3, 4 and 5, wherein the thickness is in the range of ~ 300 °. 7. An oxygen permeability of ² cc / m ² / day
(23 ° C./90% RH) or lower, wherein the transparent barrier nylon film according to claim 1, 2, 3, 4, 5, or 6. 8. A transparent barrier nylon having a structure in which a first thin film and a second thin film made of at least two or more inorganic oxides are laminated on one surface of a biaxially stretched nylon film substrate. At least a heat sink on the second thin film surface of the transparent barrier nylon film.
A laminate comprising a laminate of polyolefin resin layers having a sealing property. 9. The laminate according to claim 8, wherein the polyolefin resin layer having a heat seal property is laminated via an adhesive layer. 10. The method according to claim 1, wherein the polyolefin resin layer having heat sealability is an extruded resin layer formed by an extrusion laminating method via an anchor coating agent layer. 9. The laminate according to 8. 11. The lamination according to claim 8, wherein the biaxially stretched nylon film substrate further has at least a substrate film layer laminated on the other surface. body. 12. The laminate according to claim 11, wherein the laminate further comprises at least a heat-sealing polyolefin-based resin layer laminated on the base film layer. . 13. A transparent barrier nylon having a structure in which a first thin film and a second thin film made of at least two or more inorganic oxides are laminated on one surface of a biaxially stretched nylon film substrate. A laminate comprising at least a heat-sealing polyolefin-based resin layer laminated on the second thin film surface of the transparent barrier nylon film; Or a packaging container characterized by being made in a box.