JP5870962B2 - Gas barrier laminated film - Google Patents

Description

  The present invention relates to a gas barrier laminate film, and in particular, has a high barrier property against water vapor and oxygen, can prevent static electricity damage, and can be incinerated after use and used for packaging electronic components with little residue. The present invention relates to a gas barrier laminated film suitable as a laminated packaging material.

Conventionally, it is known that electronic parts such as a magnetic disk are damaged not only by water vapor and oxygen in the air but also by static electricity.
The technique of using half vapor deposition such as aluminum (AL) for the electrostatic shielding packaging material has been practiced for a long time. In general, as a laminated film for packaging electronic parts, one or both surfaces of a polyolefin-based substrate film containing carbon, metal or the like to impart conductivity to prevent electrostatic damage is used. Yes. However, such a conventional laminated film has a poor barrier property, and there is a problem that the electronic component is oxidized and damaged by moisture and oxygen.

In addition, a conductive layer made of carbon or metal powder coating film or metal vapor deposition film on the support surface and an AL foil having a thickness of 7 to 20 μm were bonded to the opposite side of the conductive layer, and an antistatic agent was kneaded. There is a conventional technique that protects electronic components from static electricity damage and oxidation damage caused by oxygen and moisture by using a packaging material laminated with a sealant. However, since this packaging material uses AL foil, there was a problem that the visibility of the contents could not be obtained. In addition, some current incinerators incinerate at a temperature of about 800 ° C. At this temperature, the AL foil cannot be incinerated and a large amount of residue remains.
Furthermore, with regard to a laminate in which a transparent barrier film (IB film) having transparency capable of identifying the contents is provided with an electrostatic shielding property, an inorganic oxide is vapor-deposited on a plastic substrate film, and further a barrier coat layer and half vapor deposition There has been proposed a laminate characterized by providing a layer and further laminating a barrier coat (Patent Document 1).
However, even if a half vapor deposition layer is laminated on the barrier coat layer, the gas barrier property is not improved. Therefore, this laminate has a problem that the gas barrier property is not sufficient.

JP 2004-330669 A

  The problem to be solved by the present invention is a laminate used for packaging electronic parts that has a high barrier property against water vapor and oxygen, can prevent static electricity damage, and can be incinerated after use and has little residue. It is to provide a gas barrier laminate film as a packaging material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor provided a strong adhesion treatment layer by applying an easy adhesion treatment to the surface of the gas barrier coating film in an existing transparent barrier film (IB film). By vapor-depositing a semitransparent metal thin film layer on the adhesion treatment layer, the inventors succeeded in improving the gas barrier property that could not be obtained simply by directly laminating the gas barrier coating film and the semitransparent metal thin film layer.

  That is, in the present invention, a vapor-deposited thin film layer made of an inorganic oxide or an inorganic nitride and a gas barrier coating film are sequentially laminated on at least one surface of a base film, and an easy adhesion treatment is performed on the surface of the gas barrier coating film. The present invention relates to a gas barrier laminate film characterized in that a strong adhesion treatment layer is formed and a semitransparent metal thin film layer is further laminated thereon. The present invention has the following features.

  1. In a laminated film in which a vapor-deposited thin film layer made of an inorganic oxide or an inorganic nitride is provided on at least one surface of a base film made of a plastic material, and a gas barrier coating film is further laminated thereon, the surface of the gas barrier coating film A gas barrier laminate film in which a strong adhesion treatment layer is formed by performing easy adhesion treatment, and a semitransparent metal thin film layer is further provided thereon.

  2. A gas barrier laminate film in which the easy adhesion treatment is performed by plasma treatment using oxygen, nitrogen or argon alone gas, or a mixed gas thereof.

  3. A gas barrier laminate film in which the semitransparent metal thin film layer is a layer deposited by physical vapor deposition.

  4). A gas barrier laminate film in which the semitransparent metal thin film layer is a single vapor deposition film of aluminum, nickel, or titanium, or a vapor deposition film of a mixture thereof.

5. The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents 0 or more. M represents an integer of 1 or more, and n + m represents a valence of M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier laminate film, which is a gas barrier coating film made of a gas barrier composition obtained by polycondensation of the above with a sol-gel method.

6). A gas barrier laminate film in which M in the general formula R ¹ _n M (OR ² ) _m is silicon, zirconium, titanium, or aluminum.

  7). A gas barrier laminate film in which the alkoxide is an alkoxysilane, a partial hydrolyzate of an alkoxide, or a hydrolytic condensate of an alkoxide.

8). The gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n is 0 or more) M represents an integer of 1 or more, and n + m represents a valence of M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. And a gas barrier laminate film, which is a gas barrier composition obtained by polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent.

  9. The gas barrier coating film is a base film provided with a coating film by applying a gas barrier composition at a temperature of 20 ° C. to 200 ° C. and below the melting point of the base film for 10 seconds to A gas barrier laminate film comprising a cured film that has been heat-treated for 10 minutes.

  10. A gas barrier laminate film comprising a tertiary amine in which the sol-gel catalyst is substantially insoluble in water and soluble in an organic solvent.

11. A gas barrier laminate film in which the tertiary amine is N, N-dimethylbenzylamine.

12 Water in the gas barrier composition is 0.1 to 100 per 1 mol of alkoxide.
A gas barrier laminate film used in a molar ratio.

  13. The gas barrier laminate film, wherein the gas barrier composition contains a silane coupling agent.

  14 A gas barrier laminate film in which the plastic material used for the base film made of the plastic material is polyester, polyamide or polyolefin.

  15. The gas barrier laminate film is used as an intermediate layer, and another substrate film is laminated on the intermediate layer via an adhesive layer. An antistatic coat layer or an antistatic film is used on at least the outermost surface and the innermost surface, thereby preventing antistatic. Laminated package providing layers.

The gas barrier coating film constituting the gas barrier laminated film according to the present invention is subjected to an easy adhesion treatment on the surface, whereby the surface becomes a strong adhesion treatment layer. A gas barrier that was not obtained when the gas barrier coating film and the semitransparent metal thin film layer were directly laminated by laminating the gas barrier coating film and the semitransparent metal thin film layer with the strong adhesion treatment layer interposed therebetween. The ability to show off. When the strong adhesion treatment layer is provided between the gas barrier coating film and the semitransparent metal thin film layer, the gas barrier property is at least 1.
2 times improvement.

  Thereby, the gas barrier laminate film of the present invention composed of a base film, a vapor-deposited thin film layer, a gas barrier coating film, a strong adhesion treatment layer and a translucent metal thin film layer is not only transparent to water vapor and oxygen but also transparent. It is possible to have both conductivity and conductivity that prevents electrostatic disturbance.

In addition, since it can be incinerated after use and has little residue, it is also suitable as a material for packaging electronic components.
The reason why the gas barrier property is improved by the formation of such a strong adhesion treatment layer is considered to be that the adhesion properties of the gas barrier coating film, the strong adhesion treatment layer, and the semitransparent metal thin film layer are improved.

It is a schematic sectional drawing which shows an example of the layer structure about the gas barrier laminated film which concerns on this invention. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system. It is a schematic block diagram which shows the outline | summary of the example about a plasma chemical vapor deposition apparatus.

Hereinafter, the gas barrier laminate film of the present invention will be specifically described.
1. Structure of Gas Barrier Laminate Film of the Present Invention The gas barrier laminate film according to the present invention is provided with a vapor-deposited thin film layer of an inorganic oxide or an inorganic nitride on at least one surface of a base film, and further a gas barrier coating applied thereon. In a laminated film in which films are sequentially laminated, a five-layer structure in which a strong adhesion treatment layer is formed by performing an easy adhesion treatment on the gas barrier coating film surface, and a semi-transparent metal thin film layer is further laminated thereon is a basic structure. (FIG. 1).
Further, the vapor-deposited thin film layer and the gas barrier coating film can be repeatedly laminated in this order twice or more.

When producing a laminated package using the gas barrier laminate film of the present invention, a sealant is laminated on the gas barrier laminate film of the present invention via an adhesive layer, and at least the gas barrier laminate film / adhesive layer / sealant of the present invention. The three-layer structure is used.
When manufacturing a laminated package in the form of a packaging bag, a gas barrier laminate film is used as an intermediate layer, and another substrate film is laminated on the intermediate layer via an adhesive layer, and an antistatic coat layer and an antistatic layer are formed on the outermost layer. It is preferable to laminate films.

  The layer structure of the laminated packaging bag using the gas barrier laminate film of the present invention is, for example, an antistatic coat layer / antistatic coat PET film / adhesive layer / the present gas barrier laminate film / adhesive layer / nylon (Ny). Film / Extruded PE / Antistatic PE film.

2. Base film As the base film of the present invention, it is excellent in chemical or physical strength, withstands the conditions for forming a vapor-deposited thin film layer of inorganic oxide or inorganic nitride, and does not deteriorate the characteristics of the vapor-deposited thin film layer. A film or sheet made of a plastic material that can be held can be used. Moreover, it is preferable that it is a transparent base film in order to utilize the transparency of a semi-transparent metal thin film layer.

  Specific examples of films made of such plastic materials include polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile. -Butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyurethane Films or sheets made of various plastic materials such as resin, acetal resin, and cellulose resin can be used.

  In the present invention, it is particularly preferable to use a film or sheet made of a plastic material such as a polystyrene resin, a polyamide resin, or a polyolefin resin among the films made of the plastic material.

In the present invention, the various films described above use one or more of the various resins described above, and use film forming methods such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method, A method of forming the above various resins alone, or a method of forming a multi-layer coextrusion film using two or more kinds of resins, and further forming a film using two or more kinds of resins. Various types of films are manufactured by a method such as mixing to form a film before forming, and further stretched uniaxially or biaxially using a tenter method or a tubular llama method if desired. Film.
In this invention, the film thickness of a base film is 6-188 micrometers, More preferably, it is 9-25 micrometers.

  In addition, when using one or more of the above-mentioned various resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, release properties, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying formability, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be arbitrarily added depending on the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

  Further, in the present invention, the surface of the above-mentioned various resin films or sheets may be subjected to a desired surface treatment in advance in order to improve close adhesion with an inorganic oxide or inorganic nitride deposited film, which will be described later. Layers can also be provided.

  In the present invention, examples of the surface treatment layer include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed.

  The above surface pretreatment is intended to improve the close adhesion between various resin films or sheets and the inorganic oxide or inorganic nitride deposited film described later, but improves the above close adhesion. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a vapor deposition anchor coat agent layer is arbitrarily provided on the surface of various resin films or sheets. It can also be formed into a surface treatment layer.

  Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition comprising a main component of a vehicle such as a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

3. In the present invention, the vapor deposition thin film layer laminated on the base film includes silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K). ), Tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), and other deposited thin film layers made of oxides or nitrides. be able to. In the case of depositing an inorganic nitride, SiN _x (x is 0.5 to 1.0) or the like can be used as the inorganic nitride.
Preferable examples include a deposited thin film layer made of a metal oxide of silicon (Si) or aluminum (Al).

The metal oxide vapor-deposited thin film layer is also a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide and the like, for example, SiO _x , AlO _x , MgO _x, etc. MO _X (in the formula, M represents a metal element, the value of X, each range differs by the metal element) as represented by.

In addition, as a range of the above X value, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K
) Is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1.5, titanium (Ti) is 0 to 2, lead ( Pb) can take values in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.

  In the above, when X = 0, it is a perfect metal and cannot be used because it is not transparent. Moreover, the upper limit of the range of X is a value when completely oxidized.

  Preferably, silicon (Si) having a value in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5 can be used.

  The layer thickness of the vapor-deposited thin film layer of inorganic oxide or inorganic nitride varies depending on the type of metal used, or the type of metal oxide or nitride, but is, for example, arbitrary within a range of 50 to 20000 mm, preferably 100 to 500 mm. Can be selected.

  Moreover, the metal or metal oxide to be used as an inorganic oxide layer can be used by 1 type, or 2 or more types of mixtures, and can comprise the inorganic oxide layer mixed with the dissimilar material.

Furthermore, inorganic oxide, when a silicon oxide may be a carbon-containing silicon oxide represented by SiO _x C _y. And in the formula, x is preferably in the range of 1.5 to 2.2, y is preferably in the range of 0.15 to 0.80, and x is in the range of 1.7 to 2.1. And y is 0.
More preferably, it is within the range of 39 to 0.47.
The inorganic nitride is the same as the inorganic oxide.

4). Vapor deposition method of vapor deposition thin film layer of inorganic oxide or inorganic nitride Vapor deposition of the vapor deposition thin film layer can be performed by chemical vapor deposition or physical vapor deposition, or a combination thereof. When the chemical vapor deposition method is used, vapor deposition thin film layers having different film qualities can be stacked in multiple layers.
(1) Physical vapor deposition method (Physical Vapor Deposition method, PVD method)
The physical vapor deposition method includes, for example, a vacuum deposition method, a sputtering method, an ion plating method, an ion cluster beam method, and the like.
An example of the physical vapor deposition method that can be used in the present invention will be described more specifically. FIG. 2 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an example of the inorganic oxide deposition method in the present invention.

  As shown in FIG. 2, the film to be deposited 11 is fed out from the unwinding roll 43 in the vacuum chamber 42 of the wind-up type vacuum deposition apparatus 41, and the film to be deposited 11 is passed through the guide rolls 44 and 45. To the cooled coating drum 46. Next, an evaporation source 48 heated by a crucible 47 is deposited on the film 11 to be guided guided on the cooled coating drum 46 while supplying oxygen gas or the like from an oxygen gas outlet 49 if necessary. Then, an inorganic oxide vapor-deposited thin film layer is formed through the mask 50. In the electron beam vacuum deposition method, the deposition source 48 is overheated by electron beam irradiation. Next, the film 11 to be deposited on which the inorganic oxide vapor-deposited thin film layer is laminated is wound around the take-up roll 53 via the guide rolls 51 and 52.

(2) Chemical vapor deposition (Chemical Vapor Deposition method, CVD method)
Examples of the chemical vapor deposition method used in the present invention include a plasma CVD method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method.
Specifically, a plasma CVD method (Plasma Chemical Vapor Deposition method), which is one of the chemical vapor deposition methods that can be used in the present invention, is applied to a substrate film, an inorganic oxide layer, or a gas barrier layer. On the surface of the vapor deposition surface, a monomer gas for vapor deposition of inorganic oxide is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen gas or the like is used as an oxygen supply gas. A vapor-deposited thin film layer made of an inorganic oxide is formed using a low-temperature plasma chemical vapor deposition method using a low-temperature plasma generator or the like.

In the above, as a low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, microwave plasma, etc. is used. It is desirable to use a generator.
An example of the method for forming an inorganic oxide vapor-deposited thin film layer by low-temperature plasma chemical vapor deposition in the present invention will be described. FIG. 3 is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus used in the low temperature plasma chemical vapor deposition method.

  In the present invention, as shown in FIG. 3, the film to be deposited 11 is fed out from the unwinding roll 23 disposed in the vacuum chamber 22 of the low-temperature plasma chemical vapor deposition apparatus 21. Then, it is conveyed on the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed. Oxygen gas, inert gas, monomer gas for vapor deposition, and the like are supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and a vacuum chamber is formed through the raw material supply nozzle 29 while adjusting a mixed gas composition for vapor deposition. The mixed gas composition for vapor deposition is introduced into 22, and plasma is generated by the glow discharge plasma 30 on the vapor deposition film 11 conveyed on the cooling / electrode drum 25 peripheral surface. To form an inorganic oxide vapor-deposited thin film layer. At that time, the cooling / electrode drum 25 is applied with a predetermined power from a power source 31 disposed outside the vacuum chamber 22, and a magnet 32 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted. Next, the film to be deposited 11 is wound around a winding roll 34 via an auxiliary roll 33 after forming an inorganic oxide deposited thin film layer. In the figure, 35 represents a vacuum pump.

  In the low-temperature plasma chemical vapor deposition apparatus, the inorganic oxide vapor-deposited thin film layer is formed into a thin film on the film to be vapor-deposited by using a plasma source gas, so it is dense and has few gaps. It becomes a continuous layer rich in flexibility. Therefore, the barrier property is much higher than that of the inorganic oxide vapor-deposited thin film layer formed by the conventional vacuum vapor deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness.

5. Gas barrier coating film The gas barrier coating film of the present invention is obtained by coating a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method. Thereby, the gas barrier property of a film can further be improved.
(1) Alkoxide As an alkoxide that can be used in the gas barrier composition, the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and preferably one or more alkoxides represented by it can.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum or the like can be used as the metal atom M, and alkoxysilane in which M is silicon. Is preferably used.
Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. As the partial hydrolyzate, it is not necessary that all of the alkoxy groups are hydrolyzed, and one or more of them may be hydrolyzed, or a mixture thereof. A partially hydrolyzed alkoxide having a dimer or more, specifically, a 2 to 6 mer is used.

(2) Water-soluble polymer As the water-soluble polymer, either or both of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be preferably used.
In the present invention, the content of the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide. In the above, if it exceeds 500 parts by weight, the brittleness of the barrier coating is increased, and the weather resistance and the like are also deteriorated.
In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1,000), Kuraray Poval LM-20SO (degree of saponification = 40%, degree of polymerization = 2,000) manufactured by the same company, Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) and gohsenol NH-18 (degree of saponification = 98 to 99%, degree of polymerization = 1700) and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used. Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

(3) Silane Coupling Agent In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition that forms the barrier coat according to the present invention.
In the present invention, the silane coupling agent comprises an organosilicon compound having both a hydrolyzable group that reacts with an inorganic substance and an organic functional group that reacts with an organic substance in one molecule. Examples of the hydrolyzing group that reacts with an inorganic substance include an alkoxy group such as a methoxy group and an ethoxy group, an acetoxy group, and a chloro group. Moreover, as an organic functional group which reacts with organic substance, the functional group which reacts with the hydroxyl group in a hydroxyl-containing acrylic resin or the isocyanate group of an isocyanate compound is preferable, for example, an isocyanate group, an amino group, an epoxy group, and a mercapto group are mentioned. Moreover, a vinyl group, a methacryloxy group, etc. may be sufficient.

  The organosilicon compound may have an alkyl group or a phenyl group that does not react with either an inorganic substance or an organic substance. Further, it can be mixed with a silicon compound having no organic functional group, for example, a compound such as an alkoxysilane having only a hydrolyzable group. In the present invention, the silane coupling agent may be one type or a mixture of two or more types.

Examples of the silane coupling agent used in the present invention include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, amino group-containing silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane, Contains epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Silane coupling agent, 3-mercap Examples include mercapto group-containing silane coupling agents such as topropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. It is done.

(4) Preparation of gas barrier composition Gas barrier composition comprising an alkoxide and a water-soluble polymer mixed with a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a silane coupling agent. To prepare.
For the preparation of the gas barrier composition, the amount of the above alkoxide is 0.1 mol per 1 mol of the total molar amount.
It is preferable to use 1 to 100 moles of water.
As a sol-gel method catalyst used in the preparation of a gas barrier composition, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent, for example, N, N-dimethylbenzylamine is used. As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid, and the like can be used. Furthermore, as an organic solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used, for example.

  Furthermore, regarding the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. The kind of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.

(5) Method for forming gas barrier coating film When the above gas barrier composition is applied on the inorganic oxide vapor deposition layer and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed. Thus, a transparent gas barrier coating film is formed.
Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the inorganic oxide deposition layer, the adhesion and adhesion between the inorganic oxide deposition layer and the gas barrier coating film are bonded. Good properties and the like.

By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good gas barrier properties.

  In the present invention, the inorganic oxide vapor deposition layer and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved. In addition, a better barrier property is exhibited by a synergistic effect.

In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. The dry film thickness is 0.01 ~
A barrier coat of 30 μm, preferably 0.1 to 10 μm can be formed. Furthermore,
Under normal circumstances, condensation is performed by heating and drying at a temperature of 20 to 300 ° C., preferably 20 to 200 ° C., for 3 seconds to 60 minutes, preferably 10 seconds to 10 minutes. A gas barrier coating film can be formed.

6). Strong adhesion treatment layer The strong adhesion treatment layer of the present invention is formed on the surface of the gas barrier coating film by subjecting the surface of the gas barrier coating film to an easy adhesion treatment.
By forming the strong adhesion treatment layer, it is possible to improve the gas barrier property that is not obtained when the gas barrier coating film and the semitransparent metal thin film layer are directly laminated.
The easy adhesion treatment is performed by plasma treatment using oxygen, nitrogen, or argon alone or a mixed gas thereof.
The easy adhesion treatment uses a glow discharge plasma generator, power of 0.5 to 20 kw, oxygen gas or argon gas alone or a mixed gas thereof, and a mixed gas pressure of 2 to 100 × 10 ⁻³ mbar, treatment. A strong adhesion treatment layer was formed by oxygen plasma or argon gas single plasma treatment or oxygen / argon mixed gas plasma treatment at a speed of 100 to 600 m / min.

7). Semi-transparent metal thin film layer The semi-transparent metal thin film layer can be vapor-deposited by chemical vapor deposition or physical vapor deposition, or in combination, as with the vapor deposition thin film layer described above.
The translucent metal thin film layer of the present invention is formed by vapor deposition of metals such as Al, Ni and Ti by the above method, but by adjusting the light transmittance, the visibility of the contents is obtained, And it can be set as the layer (semi-transparent metal thin film layer) from which a certain amount of light-shielding property is acquired.
Specifically, the light transmittance is preferably 20% to 60%. For this purpose, the thickness of the semitransparent vapor-deposited film is in the range of 20 to 150 mm, and the degree of vacuum is 1 to 100 × 10 ^−4. It is preferable to deposit under mBar vacuum conditions.
As a method for producing the semitransparent metal thin film layer, for example, a vacuum deposition method using an electron beam (EB) heating method is preferable.

8). Adhesive layer, another substrate film, antistatic coat layer and antistatic film (1) Adhesive layer Examples of the adhesive constituting the adhesive layer include polyvinyl acetate adhesive, ethyl acrylate, and butyl. , 2-ethylhexyl ester and other homopolymers, or polyacrylic acid ester adhesives comprising these and copolymers of methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene and vinyl acetate, acrylic Ethylene copolymer adhesives, such as copolymers with monomers such as ethyl acid, acrylic acid and methacrylic acid, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, urea resins or melamines Amino resin adhesives made of resin, phenol resin adhesives, epoxy adhesives Agent, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate, low melting point glass, etc. Inorganic adhesives and other adhesives can be used.

The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
The adhesive can be applied, for example, by a roll coating method, a gravure roll coating method, a kiss coating method, or other coating methods, and the coating amount is 0.1 to 0.1.
A position of 10 g / m ² (dry state) is desirable.

(2) Another base film A base material consists of a polymer film. Specifically, polyester film made of polyethylene terephthalate (PET) or polyethylene naphthalate, polyolefin film made of polyethylene, polypropylene, etc., polystyrene film, polyamide film, polyvinyl chloride film, polycarbonate film, polynitriloacrylic film, polyimide film And biodegradable plastic films such as polylactic acid films. These may be stretched or unstretched, but those having excellent mechanical strength and those having dimensional stability are preferably used. In these, the polyethylene terephthalate arbitrarily extended | stretched to biaxial direction from surfaces, such as heat resistance, is more preferable. Further, a thin film layer made of various known additives and stabilizers such as an antistatic agent, an anti-ultraviolet agent, a plasticizer, a lubricant and the like may be provided on the surface of the base material. In order to improve the adhesion to the thin film layer formed on the substrate, corona treatment, low temperature plasma treatment, chemical treatment, solvent treatment, etc. may be appropriately performed as pretreatment.

Further, a polyamide layer may be provided between the heat seal layer and the gas barrier coating layer in order to give a waist when used as a packaging bag and to give resistance to piercing and friction. Specifically, it may be formed of a known polyamide resin such as 6-nylon obtained by ε-caprolactam ring-opening polymerization reaction, 6,6-nylon obtained by polycondensation reaction of hexamethylenediamine and adipate. . More specifically, these polyamide resins processed into a film may be provided by being laminated.

  In particular, those arbitrarily stretched in the biaxial direction are preferably used because they are excellent in mechanical strength and dimensional stability. A thin film layer may be further provided on the surface of the polyamide layer with various known additives and stabilizers such as an antistatic agent, an anti-ultraviolet agent, a plasticizer, a lubricant, and the adhesion to the thin film. In order to improve the quality, corona treatment, low-temperature plasma treatment, ion bombardment treatment, etc. may be performed as pretreatment, and further chemical treatment, solvent treatment, etc. may be performed.

(3) Antistatic coating layer The component of the antistatic coating agent constituting the electrostatic antistatic layer is not particularly limited as long as it reduces the surface resistivity. For example, glycerin fatty acid ester, polyoxyethylene alkyl ether, poly Oxyethylene alkyl phenyl ether, alkyl diethanol amine, hydroxyalkyl monoethanol amine, polyoxyethylene alkyl amine, alkyl diethanol amide, alkyl sulfonate, alkyl benzene sulfonate, alkyl phosphate, tetraalkyl ammonium salt, alkyl betaine, alkyl imidazolium betaine Etc.

  Conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method, a gravure printing method and the like that are usually used can be used as a method for applying the antistatic coating agent. The thickness of the coating film varies depending on the composition of the antistatic coating agent, the coating processing machine, and the processing site conditions, but if it is a method that can be applied so as to express the expected function when used as a packaging bag, It is not particularly limited.

(4) Antistatic film As the thermoplastic resin constituting the antistatic film, any conventionally known resin used for forming a film can be used. Preferred are low density polyethylene, medium density polyethylene, high Examples thereof include high density polyethylene, linear low density polyethylene, polypropylene, copolymers of ethylene and vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, and the like, and polyolefin-based thermoplastic resins such as ionomers.
As the antistatic agent to be included in the thermoplastic resin, any conventionally known antistatic agent can be used, but preferred examples include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, Surfactant such as polyglycerin fatty acid ester, propylene glycol fatty acid ester, higher alcohol fatty acid ester, polyhydric alcohol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phenyl ether and the like A type of antistatic agent.

The method for adding the antistatic agent to the thermoplastic resin and the film forming method may be a conventionally known method. For example, a predetermined amount of the antistatic agent is sufficiently mixed with the resin pellets and melt-kneaded in an extruder. Examples thereof include a method of forming a film through an inflation die, a method of forming a film in the same manner using a master batch containing an antistatic agent at a high concentration, and a method of adding an antistatic agent and a method of forming a film are not particularly limited.
In addition, as the sealant layer that is the innermost layer, a polyolefin-based thermoplastic resin is provided as an adhesive layer when forming a bag-like package or the like, for example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, Resins such as ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, and their metal cross-linked products are used.

  Although the thickness is determined according to the purpose, it is generally in the range of 15 to 200 μm, and electrical characteristics (antistatic) may be imparted.

Hereinafter, the present invention will be specifically described by way of examples.
I. Preparation of laminated film [Example 1]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film. The above-mentioned biaxially stretched polyethylene terephthalate film was mounted on a feed roll of a take-up vacuum deposition apparatus. Next, this was fed out, and the following corona discharge treatment surface of the biaxially stretched polyethylene terephthalate film was subjected to the following vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source. An aluminum oxide vapor deposition film having a thickness of 200 mm was formed according to the vapor deposition conditions.
(Deposition conditions)
Degree of vacuum in the deposition chamber after introducing oxygen gas: 2 × 10 ⁻⁴ mbar
Degree of vacuum in the take-up chamber: 2 × 10 ^-2 mbar
Electron beam power: 25kW
Film transport speed: 240 m / min Deposition surface: Corona discharge treatment surface

Then, a glow discharge plasma generator is used on the vapor deposition film surface of aluminum oxide, and a mixed gas consisting of power 9 kw, oxygen gas: argon gas = 7.0: 2.5 (unit: slm) is used, and the mixed gas An oxygen / argon mixed gas plasma treatment was performed at a pressure of 6 × 10 ⁻² mbar and a treatment speed of 420 m / min to form a plasma treated surface in which the surface tension of the aluminum oxide deposition film surface was improved by 54 dyne / cm or more.

(2) On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in a hydrolyzed solution composed of orthoethyl silicate (manufactured by Tama Kagaku Co., Ltd.), isopropyl alcohol, 0.5 N hydrochloric acid aqueous solution, ion-exchanged water, and silane coupling agent b. A polyvinyl alcohol aqueous solution was added and stirred to obtain a colorless and transparent gas barrier coating solution.

Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier coating liquid produced in the above (2) by a gravure roll coating method, and then heat-treated at 150 ° C. for 60 seconds to obtain a thickness. A gas barrier coating film having a thickness of 0.2 μm (in the dry operation state) was formed to produce a laminated film.

(3) Next, the laminated film prepared above was mounted on a delivery roll of a take-up vacuum deposition apparatus. Next, this was fed out, and a glow discharge plasma generator was used on the gas barrier coating film surface of the laminated film, the power was 9 kw, oxygen gas: argon gas = 7.0.
: Using a mixed gas consisting of 2.5 (unit: slm), mixed gas pressure 6 × 10 ⁻² mbar,
An oxygen / argon mixed gas plasma treatment was performed at a treatment speed of 240 m / min to form a strong adhesion treatment layer.

(4) Thereafter, the aluminum having a film thickness of 100 mm is deposited on the above-mentioned strong adhesion treatment layer by vacuum deposition using an electron beam (EB) heating method using aluminum as a deposition source under the following deposition conditions. A film was formed to prepare a gas barrier laminate film of the present invention.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 1 × 10 ⁻⁴ mbar
Degree of vacuum in the take-up chamber: 2 × 10 ^-2 mbar
Electron beam power: 20kW
Film transport speed: 240 m / min Deposition surface: Strong adhesion treatment surface

[Example 2]
The strong adhesion treatment conditions described in (3) of Example 1 are as follows: power 9 kw, nitrogen gas: argon gas = 60: 3.0 (unit: slm) mixed gas, mixed gas pressure 6 × 10 ⁻² mbar
The gas barrier laminate film of the present invention was manufactured by changing to nitrogen / argon mixed gas plasma treatment at a treatment speed of 240 m / min to form a strongly-adhesive treatment layer, and otherwise performing the same test as in Example 1. .

[Example 3]
The strong adhesion treatment conditions described in (3) of Example 1 were as follows: power 9 kw, use of a mixed gas consisting of argon gas = 70 (unit: slm), mixed gas pressure 6 × 10 ⁻² mbar, treatment speed 240 m / min. The gas barrier laminate film of the present invention was produced in the same manner as in Example 1 except that a strong adhesion treatment layer was formed instead of the argon gas plasma treatment.

[Example 4]
The strong adhesion treatment conditions described in (3) of Example 1 are as follows: a power of 4 kW, use of a mixed gas consisting of argon gas = 70 (unit: slm), a mixed gas pressure of 6 × 10 ⁻² mbar, and a treatment speed of 240 m / min. The gas barrier laminate film of the present invention was produced in the same manner as in Example 1 except that a strong adhesion treatment layer was formed instead of the argon gas plasma treatment.

[Comparative Example 1]
A gas barrier laminate film was produced by performing the same test as in Example 1 except that the strong adhesion treatment described in (3) of Example 1 and the semipermeable metal vapor deposition described in (4) were not performed.

[Comparative Example 2]
A gas barrier laminate film was produced in the same manner as in Example 1 except that the strong adhesion treatment described in (3) of Example 1 was not performed.

[Comparative Example 3]
A gas barrier laminate film was produced in the same manner as in Example 1 except that the transparent vapor-deposited film described in (1) of Example 1 and the gas barrier coating layer described in (2) were not applied.

II. Production of packaging material Using the laminated films produced in Examples 1 to 4 and Comparative Examples 1 to 3, packaging materials were produced as follows.
(1) Composition of packaging material:
Antistatic coating (static) PET film 12 / adhesive / laminated film prepared in Examples or Comparative Examples / adhesive / nylon (Ny) 25 / extruded PE20 / antistatic film PE40

(2) Preparation of packaging material (a) Toyobo T-6140, 12 μm was used as anti-static PET, and a commonly used adhesive was applied to the corona-treated surface of the film by a gravure roll method with a thickness of 4.0 g. / Square meter (dry)
The film was applied at a thickness of 5 mm, and dry lamination was performed with the Al vapor deposition surface side of the example or comparative film facing each other.
(B) An adhesive generally used in the same manner as in (a) is applied to the base material surface of the example of the laminate or the comparative example film of (a) by a gravure roll method with a thickness of 4.0 g / square meter ( (Dry), and ONBC 25 μm manufactured by Unitika Ltd. was dry-laminated.
(C) Further, a general anchor coating agent is applied to the corona-treated surface of the nylon film of the laminate (b) by a gravure roll method to a thickness of 0.5 g / square meter (dry), and the anchor The coating surface and an antistatic polyethylene film L-140 40 μm manufactured by Aicero Chemical Co., Ltd. were opposed to each other, and polyethylene was extruded and laminated with a film thickness of 20 μm by a melt extrusion method between them. A package was obtained.

III. The following tests were conducted using the laminated films prepared in Examples 1 to 4 and Comparative Examples 1 to 3. The results are shown in Table 2.
(A) Water vapor permeability measurement: The water vapor permeability was measured using a water vapor permeability measuring device (PARMATRAN-W3 / 31, manufactured by Modern Control Co., Ltd.) in an atmosphere of 40 ° C. and 90% RH.
(B) Degree of improvement in moisture resistance: The degree of improvement in moisture resistance is determined according to the “moisture resistance before treatment of the semipermeable metal film in the laminated film produced in Comparative Example 1” as “in each example. It was calculated by dividing by “moisture resistance after treatment of semipermeable metal film in laminated film”.
(C) Static electricity shielding property: Measured when an external voltage of 1000 V was applied based on EIA 541 Appendix E.
(D) Laminate strength: The laminate strength was measured by a method using T-peeling after fixing a sample cut into a strip shape having a width of 15 mm to a tensile tester (a tensile tester manufactured by Orientec Co., Ltd.).

  The laminated film of the present invention was excellent in barrier properties and electrostatic shielding properties as compared with the laminated film of the comparative example, and at the same time, the laminate strength was also excellent.

A: Gas barrier laminate film 1: Base film 2: Deposition thin film layer 3: Gas barrier coating film 4: Strong adhesion treatment layer 5: Translucent metal thin film layer 11: Deposition film 21: Low temperature plasma chemical vapor deposition apparatus 22 42: Vacuum chamber 23, 43: Unwinding roll 24, 33: Auxiliary roll 25: Cooling / electrode drum 26, 27: Gas supply device 28: Raw material volatilization supply device 29: Raw material supply nozzle 30: Glow discharge plasma 31: Power source 32: Magnet 34, 53: Winding roll 35: Vacuum pump 41: Winding type vacuum deposition apparatus 44, 45, 51, 52: Guide roll 46: Coating drum 47: Crucible 48: Deposition source 49: Oxygen gas outlet 50 :mask

Claims (13)

On at least one surface of a base material film made of a plastic material, a deposited thin film layer made of an inorganic oxide or an inorganic nitride, and a gas barrier coating film thereon,
A strong adhesion treatment layer formed on the surface of the gas barrier coating film and subjected to plasma treatment with a single gas of oxygen, nitrogen or argon, or a mixed gas thereof, and using a glow discharge plasma generator and power 4 ~ 20kw, gas pressure 2-100x10 ^-3 mbar, a layer subjected to easy adhesion treatment at a treatment speed of 100 to 600 m / min,
Furthermore, it is a gas barrier laminated film in which a translucent metal thin film layer is disposed thereon,
The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (Wherein R ¹ And R ² Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M). A gas barrier property which is a coating film made of a gas barrier composition obtained by polycondensation of one or more alkoxides with a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer by a sol-gel method. Laminated film. The gas barrier laminate film according to claim 1, wherein the semitransparent metal thin film layer is a physical vapor deposition layer .   The gas barrier laminate film according to claim 1, wherein the semitransparent metal thin film layer is a single vapor deposition film of aluminum, nickel, or titanium, or a vapor deposition film of a mixture thereof. The gas barrier laminate film according to claim 1, wherein M in the general formula R ¹ _n M (OR ² ) _m is silicon, zirconium, titanium, or aluminum.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the alkoxide is composed of alkoxysilane, a partial hydrolyzate of alkoxide, or a hydrolyzed condensate of alkoxide. The gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n is 0 or more) M represents an integer of 1 or more, and n + m represents a valence of M), a polyvinyl alcohol resin and / or ethylene / vinyl alcohol. And a gas barrier composition obtained by polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. The gas barrier laminate film according to any one of claims 1 to 5. The gas barrier laminate film according to any one of claims 1 to 6, wherein the gas barrier coating film is a cured film obtained by heat-treating a gas barrier composition .   The gas barrier according to any one of claims 1 to 7, wherein the sol-gel catalyst is a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. Laminated film.   The gas barrier laminate film according to claim 8, wherein the tertiary amine comprises N, N-dimethylbenzylamine.   The water in the said gas barrier composition is used in the ratio of 0.1-100 mol with respect to 1 mol of alkoxides, The gas barrier laminated film of any one of Claims 1-9 characterized by the above-mentioned.   The gas barrier laminate film according to any one of claims 1 to 10, wherein the gas barrier composition contains a silane coupling agent.   The gas barrier laminate film according to any one of claims 1 to 11, wherein the plastic material used for the base film made of the plastic material is polyester, polyamide or polyolefin. The gas barrier laminate film according to any one of claims 1 to 12 as an intermediate layer, still another substrate film through an adhesive layer to Re this is laminated, at least the outermost surface and the innermost surface of the charge A laminated package comprising an antistatic coating layer or an antistatic layer using an antistatic film.

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