JP2010089397A - Gas-barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier laminated film which has high gas-barrier properties, suppresses a static electricity obstacle, reduces an incineration residue after being used, and has flexibility and impact resistance to elongation and folding of a film. <P>SOLUTION: On at least one side of a base film made of a polyamide, a transparent gas-barrier layer 2, a gas-barrier coating film 3, and a strong adhesion processed layer 4 are formed, and a translucent metal thin film layer 5 is further provided thereon to produce the gas-barrier laminated film. <P>COPYRIGHT: (C)2010,JPO&INPIT

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 has been a problem that the visibility of the contents cannot 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.
In addition, if the flexibility of the film is not sufficient, there is a problem that the film has cracks due to elongation or bending of the film, and the barrier property of the film is lowered. Therefore, it was also important to give the film impact resistance and flexibility.
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 that the barrier property against water vapor and oxygen is high, and has flexibility to prevent the barrier property from being lowered due to stretching or bending of the film, can prevent electrostatic failure, and An object of the present invention is to provide a gas barrier laminated film as a laminated packaging material that can be used for packaging electronic components that can be incinerated after use and has little residue.

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.
In addition, in order to prevent the film from being cracked due to stretching or bending of the film, the present inventor used a chemical vapor deposition method (CVD) as a transparent gas barrier layer deposited on a substrate in an existing transparent barrier film (IB film). The organic silicon oxide film deposited using the method is provided, and the gas barrier laminate film of the present invention has been successfully provided with the flexibility to prevent cracks due to the elongation of the film.

  That is, the present invention provides an easy adhesion treatment on the surface of the gas barrier coating film in a laminated film in which a transparent gas barrier layer is provided on at least one surface of a base film made of polyamide and a gas barrier coating film is further laminated thereon. A gas barrier laminate film characterized in that a strong adhesion treatment layer is formed by further forming a semi-transparent metal thin film layer thereon, the transparent gas barrier layer comprising silicon oxide, graphite , A continuous layer containing carbon alone or / and a carbon compound bonded to a silicon oxide molecular chain in either diamond or fullerene form, and carbon from the surface of the transparent gas barrier layer toward the depth direction. The present invention relates to a gas barrier laminate film characterized in that the content is reduced. The present invention has the following features.

  1. In a laminated film in which a transparent gas barrier layer is provided on at least one surface of a base film made of polyamide and a gas barrier coating film is further laminated thereon, a strong adhesion is obtained by subjecting the surface of the gas barrier coating film to an easy adhesion treatment. A gas barrier laminated film in which a treatment layer is formed and a semitransparent metal thin film layer is further provided thereon, wherein the transparent gas barrier layer is silicon oxide and is in the form of graphite, diamond, or fullerene A gas barrier laminate film which is a continuous layer containing carbon alone and / or a carbon compound bonded to a silicon oxide molecular chain, and whose carbon content decreases from the surface of the transparent gas barrier layer in the depth direction. .

  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 composed of alkoxysilane, a partial hydrolyzate of alkoxide, or a hydrolytic condensate of 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 A gas barrier laminate film in which water in the gas barrier composition is used at a ratio of 0.1 to 100 moles per mole of alkoxide.

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

14 A gas barrier laminate film in which an antistatic coating agent is applied to the opposite side of the surface of the base film made of polyamide on which the transparent gas barrier layer is laminated, and the surface resistivity is 10 ¹² Ω / □ or less.

  15. A laminate package using the gas barrier laminate film.

  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 can be improved by at least 1.2 times compared to the case where the strong adhesion treatment layer is not provided.

  In addition, the transparent gas barrier layer constituting the gas barrier laminate film according to the present invention has a silicon oxide and a carbon compound bonded to a single carbon and / or silicon oxide molecular chain that is in the form of graphite, diamond or fullerene. The carbon content was decreased from the surface of the transparent gas barrier layer toward the depth direction. Thereby, the continuous layer of silicon oxide constituting the transparent gas barrier layer is dense and has an extremely high barrier property, and further contains at least one kind or two or more kinds of elements of carbon, hydrogen, silicon and oxygen. According to the compound, the continuous layer of silicon oxide has excellent impact resistance. Further, the content of the above compound in the transparent gas barrier layer decreases from the surface of the transparent gas barrier layer in the depth direction, that is, the content is the largest on the outermost surface of the transparent gas barrier layer, and the base film Therefore, the impact resistance of the outermost surface of the transparent gas barrier layer where cracks are most likely to occur is improved, and the adhesion between the base film and the silicon oxide film is strengthened.

  The impact resistance is improved by the present invention and the flexibility of the film is also improved. As a result, it is possible to prevent the occurrence of cracks due to the elongation or bending of the film, and to prevent the barrier property of the film from being lowered.

  Thus, the gas barrier laminate film of the present invention composed of a base film made of polyamide, a transparent gas barrier layer, a gas barrier coating film, a strong adhesion treatment layer, and a semi-transparent metal thin film layer has a barrier property and resistance to water vapor and oxygen. It has not only impact properties but also flexibility to prevent the barrier properties from being lowered due to stretching or bending of the film, and it can have both transparency and conductivity that prevents electrostatic damage.

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 forming such a strong adhesion treatment layer is considered to be because the adhesion properties of the gas barrier coating film, the strong adhesion treatment layer, and the semitransparent metal thin film layer are improved.

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 a laminate in which a transparent gas barrier layer is provided on at least one surface of a base film made of polyamide, and a gas barrier coating film is further laminated thereon. The film has a five-layer structure in which a strong adhesion treatment layer is formed by subjecting the gas barrier coating film surface to an easy adhesion treatment, and a semitransparent metal thin film layer is further laminated thereon (Fig. 1).
In addition, the transparent gas barrier 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 is laminated. Used in a three-layer structure.
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 and the like.

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 polyamide-based resin 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.

  In the present invention, among films made of the above plastic material, it is particularly preferable to use a film or sheet made of a biaxially stretched polyamide resin plastic material having pinhole resistance.

  In the present invention, in addition to a polyamide resin, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin), an 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 resins An acetal resin, a cellulose resin, or the like can be used.

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 to the polyamide-based resin, one or more of the above-mentioned various resins are used, and when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, Various plastic compounding agents and additives can be added for the purpose of improving and modifying antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. The addition amount can be arbitrarily added from a very small amount to several tens of percent 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.

  In the present invention, the surface of the above-mentioned various resin films or sheets is provided with a desired surface treatment layer in advance in order to improve close adhesion with a deposited film of a transparent gas barrier layer described later. I can leave.

  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-mentioned surface pretreatment is for improving the tight adhesion between various resin films or sheets and the vapor deposition film of the transparent gas barrier layer described later, but as a method for improving the above-mentioned tight adhesion, In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a deposition anchor coat agent layer may be arbitrarily formed in advance on the surface of various resin films or sheets. The surface treatment layer can also be used.

  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. Transparent gas barrier layer In the present invention, the transparent gas barrier layer laminated on the base film is composed of a silicon oxide and a carbon compound bonded to a single carbon and / or silicon oxide molecular chain in the form of graphite, diamond or fullerene. And the carbon content decreases in the depth direction from the surface of the transparent gas barrier layer.
The transparent gas barrier layer is a continuous layer mainly composed of silicon oxide. The silicon oxide constituting the transparent gas barrier layer is a thin film of SiO _x (x = 1 to 2), preferably a continuous layer, and has a thickness of about 10 to 3000 mm, preferably about 60 to 400 mm. In particular, from the viewpoint of transparency, the silicon oxide continuous layer is preferably a thin film of SiO _x (x = 1.7 to 2).

In addition to the silicon oxide, the transparent gas barrier layer contains at least one compound composed of one or more elements of carbon, hydrogen, silicon and oxygen. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a single carbon is in the form of graphite, diamond, or fullerene, and further containing a raw material organosilicon compound or a derivative thereof There is. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the transparent gas barrier layer can be changed by changing the conditions of the vapor deposition process. The content of these compounds in the transparent gas barrier layer is 0.1 to 50%, preferably about 5 to 20%. When the content is less than 0.1%, the impact resistance and spreadability of the transparent gas barrier layer are insufficient, cracks are observed due to bending, and high barrier properties can be stably maintained. Disappear. On the other hand, when the content exceeds 40%, the barrier properties are undesirably lowered. Furthermore, in this invention, it is preferable to reduce content of said compound in a transparent gas barrier layer toward the depth direction from the surface of a transparent gas barrier layer. Thereby, the continuous layer of silicon oxide on the outermost surface of the transparent gas barrier layer is improved in impact resistance by the above compound, while the content of the above compound is small at the interface with the base film, so Adhesion with the material continuous layer becomes strong.
The vapor deposition of the transparent gas barrier layer can be performed by a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method), and vapor deposition thin film layers having different film qualities can be laminated in multiple layers. 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.

An example of a plasma CVD method (Plasma Chemical Vapor Deposition method), which is one of chemical vapor deposition methods that can be used in the present invention, will be described. FIG. 2 is a view showing an example of a plasma CVD (Chemical Vapor Deposition) apparatus used for vapor deposition of the transparent gas barrier layer of the present invention. In FIG. 2, the plasma CVD apparatus 11 includes a chamber 12, a supply roller 13 disposed in the chamber 12, a winding roller 14, a cooling / electrode drum 15, and an auxiliary roller 16, and the cooling / electrode drum 15 is a power source. 17, and the inside of the chamber 12 can be set to a desired degree of vacuum by a vacuum pump 18. Further, an opening of a raw material supply nozzle 19 is located in the vicinity of the cooling / electrode drum 15 in the chamber 12, and the other end of the raw material supply nozzle 19 is volatilized in the raw material disposed outside the chamber 12. The supply device 21 and the gas supply device 22 are connected. Further, a magnet 23 is installed in the vicinity of the cooling / electrode drum 15 to promote the generation of plasma.
The raw material of the base film 1 is mounted on the supply roller 13 of the plasma CVD apparatus 11 as described above, and reaches the take-up roller 14 via the auxiliary roller 16, the cooling / electrode drum 15, and the auxiliary roller 16. Such an original fabric conveyance path is formed.

Next, the inside of the chamber 12 is depressurized by the vacuum pump 18 so that the degree of vacuum is 10 ⁻¹ to 10 ⁻⁸ torr, and preferably the degree of vacuum is 10 ⁻³ to 10 ⁻⁷ torr. Then, the organic silicon compound as the raw material is volatilized in the raw material volatilization supply device 21 and mixed with the oxygen gas and the inert gas supplied from the gas supply device 22, and this mixed gas is supplied into the chamber 12 through the raw material supply nozzle 19. To introduce. In this case, the content of the organosilicon compound in the mixed gas may be 1 to 40%, the content of oxygen gas may be 10 to 70%, and the content of inert gas may be 10 to 60%. The mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14.

On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power source 17, a glow discharge plasma P is established in the vicinity of the opening of the raw material supply nozzle 19 in the chamber 12 and the cooling / electrode drum 15. The The glow discharge plasma P is derived from one or more gas components in the mixed gas. In this state, the base film 1 is transported at a constant speed, and the transparent gas barrier layer 2 composed of a continuous layer of silicon oxide is formed on the base film 1 on the peripheral surface of the cooling / electrode drum 15 by glow discharge plasma P. To do. The degree of vacuum in the chamber 12 at this time is 10 ⁻¹ to 10 ⁻⁴ torr, preferably 10 ⁻¹ to 10 ⁻² torr. Moreover, the conveyance speed of the base film 1 shall be 10-300 m / min, Preferably it is 50-150 m / min.
The base film 1 on which the transparent gas barrier layer is thus formed is wound up on the winding roller 14.

In the formation of the transparent gas barrier layer 2 in the plasma CVD apparatus 11 as described above, a thin film is formed on the base film 1 in the form of SiO _x while oxidizing the plasma-formed source gas with oxygen. The oxide thin film becomes a dense continuous layer with few gaps. Therefore, the barrier property of the transparent gas barrier layer 2 is much higher than the barrier property of a silicon oxide film formed by conventional vacuum deposition, and a sufficient barrier property can be obtained with a thin layer thickness. Further, since the surface of the base film 1 is cleaned by SiO _x plasma and polar groups and free radicals are generated on the surface of the base film 1, the adhesion between the formed silicon oxide thin film and the base film 1 Is expensive. Further, as described above, the degree of vacuum at the time of forming the silicon oxide thin film is 10 ⁻¹ to 10 ⁻⁴ torr, preferably 10 ⁻¹ to 10 ⁻² torr. Since the degree of vacuum is low compared to the degree of vacuum (10 ^-4 to 10 ^-5 torr) at the time, the vacuum state setting time when the base film is replaced can be shortened, and the degree of vacuum is also stable. Easy and stable film formation process.

  Examples of the organosilicon compound used in the present invention include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, Examples include diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Of these, 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane are particularly preferably used. These organosilicon compounds are liquid at normal temperature and normal pressure.

The property of the transparent gas barrier layer of the gas barrier laminate film produced according to the present invention is determined by the value of x of the composition SiO _x of the silicon oxide continuous layer constituting the transparent gas barrier layer, and the layer thickness. A good silicon oxide continuous layer can be formed by optimizing the conveyance speed, the electric power at the time of plasma generation, and the mixing ratio of the mixed gas.

4). 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 A gas barrier composition obtained by mixing an alkoxide and a water-soluble polymer 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, it is preferable to use water in a proportion of 0.1 to 100 mol with respect to 1 mol of the total molar amount of the alkoxide.
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. Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid. 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, the effect of better barrier properties can be exhibited by a synergistic effect.

  In the present invention, the method for applying the gas barrier composition is, for example, once or a plurality of times by an application means such as a roll coat such as a gravure roll coater, spray coat, dipping, brush, bar coat, applicator or the like. With this coating, a barrier coat having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed. Furthermore, the condensation is carried out by heating and drying in a normal environment 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. The gas barrier coating film of the invention can be formed.

5). 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.

6). Translucent Metal Thin Film Layer The translucent metal thin film layer can be deposited by chemical vapor deposition or physical vapor deposition, or in combination. The chemical vapor deposition method is as described for the vapor deposition method of the transparent gas barrier layer. The physical vapor deposition method (Physical Vapor Deposition method, PVD method) used in the present invention includes, for example, a vacuum vapor deposition method, a sputtering method, and the like. Method, ion plating method, ion cluster beam method and the like. A vacuum deposition method, which is one of physical vapor deposition methods that can be used in the present invention, will be described. FIG. 3 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an example of a method for depositing a semitransparent metal thin film layer in the present invention.

  As shown in FIG. 3, in the vacuum chamber 42 of the take-up vacuum deposition apparatus 41, the base film 1 is fed out from the unwinding roll 43, and the base film 1 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 evaporated on the substrate film 1 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 base film 1 on which the inorganic oxide vapor-deposited thin film layer is laminated is wound around the winding roll 53 via the guide rolls 51 and 52.

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.

7). Adhesive Layer, Another Substrate Film, Antistatic Coat Layer, and Antistatic Film (1) Adhesive Layer As the adhesive constituting the adhesive layer, a general-purpose dry laminate adhesive can be used. For example, polyvinyl acetate adhesives, homopolymers such as ethyl acrylate, butyl, 2-ethylhexyl ester, or copolymers of these with methyl methacrylate, acrylonitrile, styrene, etc. Adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives composed of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, cellulose adhesives, polyester adhesives , Polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive , Chloroprene rubber, nitrile rubber, styrene-butadiene rubber Rubber adhesive comprising a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of a low-melting-point glass or the like, may be used other adhesives.

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 by, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, and the coating amount is 0.1 to 10 g / m ² (dry state). The position 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 polyamide film having a thickness of 25 μm is used, and this is mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and on the corona discharge treated surface of the above biaxially stretched polyamide film under the following conditions: Then, a vapor-deposited film of silicon oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150m / min
Power: 35kW

After that, a glow discharge plasma generator is used on the vapor deposition film surface of silicon oxide, a mixed gas consisting of power 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: slm) is used, and the mixed gas 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 deposited silicon oxide film surface was improved by 54 dyne / cm or more.

  (2) On the other hand, according to the composition shown in Table 1, 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 of 0.2 μm (dry operation state) was formed to produce a gas barrier laminated film.

(3) Next, the gas barrier laminate film prepared above was mounted on a feed 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 gas barrier laminate film, and the power was 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: slm). Using this mixed gas, oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a processing speed of 240 m / min to form a strongly adherent treated layer.

(4) Thereafter, the aluminum having a film thickness of 100 mm is vapor-deposited by the following vapor deposition conditions by the vacuum vapor deposition method using the electron beam (EB) heating method, using aluminum as the vapor deposition source on the above-mentioned tight adhesion treatment surface. 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 were carried out using a mixed gas consisting of power 9 kw, nitrogen gas: argon gas = 60: 3.0 (unit: slm), and mixed gas pressure 6 × 10 ^−2. 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 by changing to a nitrogen / argon mixed gas plasma treatment at mbar and a treatment speed of 240 m / min.

[Example 3]
The strong adhesion treatment conditions described in (3) of Example 1 were performed using a mixed gas consisting of power 9 kw, argon gas = 70 (unit: slm), mixed gas pressure 6 × 10 ⁻² mbar, and processing 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 the argon gas plasma treatment was performed to form a strong adhesion treatment layer.

[Example 4]
The strong adhesion treatment conditions described in (3) of Example 1 use a mixed gas consisting of power 4 kW, 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 the argon gas plasma treatment was performed to form a strong adhesion treatment layer.

[Comparative Example 1]
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 and the semi-transmissive 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 (1) 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 deposition film described in (1) of Example 1 and the gas barrier coating film described in (2) were not applied.

[Comparative Example 4]
The method for producing a transparent vapor-deposited film described in Example 1 uses a biaxially stretched polyamide film having a thickness of 25 μm as a base film. First, the above-described biaxially stretched polyamide film is sent out by a take-up vacuum deposition apparatus. Mounted on a roll. Next, this was fed out, and the following vapor deposition was performed by a vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas to the corona discharge treatment surface of the biaxially stretched polyamide film using aluminum as a vapor deposition source. Depending on the conditions, a vapor deposition film of aluminum oxide having a thickness of 200 mm was formed.
(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 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 deposited film surface of aluminum oxide was improved by 54 dyne / cm or more.

  Thereafter, after the step of forming the gas barrier coating film described in (2), a gas barrier laminated film was produced in the same manner as in Example 1.

[Comparative Example 5]
After forming the transparent barrier film described in Example 1, the gas barrier coating film described in (2) was formed to produce a gas barrier laminated film.

II. Preparation of packaging material Using the laminated films prepared in Examples 1 to 4 and Comparative Examples 1 to 5, packaging materials were prepared 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 thickness of 1.0 g / square meter (dry) of a general antistatic coating agent by gravure roll method on the base film surface (surface opposite to the deposition surface) of the film of the present invention. And a desired antistatic coating layer was provided.
Further, a general anchor coating agent is applied to the Al vapor deposition surface side of the present invention by a gravure roll method at a thickness of 0.5 g / square meter (dry). Electrostatic-preventing polyethylene film L-140 was opposed to 60 μm, and polyethylene was extruded and laminated with a film thickness of 20 μm by a melt extrusion method to obtain a package using the film described in Examples or Comparative Examples.

III. The following tests were performed using the laminated films prepared in Examples 1 to 4 and Comparative Examples 1 to 5. 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.).
(E) Spreadability: Using a tensile tester Tensilon manufactured by Orientec Co., Ltd., the barrier film is pulled 3% and held in that state for 30 seconds. Then, it returned to the original and observation (crack) of the surface state was performed with the optical microscope and the scanning electron microscope. At the same time, the water vapor permeability was also measured.

  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, laminated strength and spreadability were also excellent. Therefore, compared with the conventional one, the effect of suppressing the deterioration of moisture resistance due to the elongation or bending of the film is exhibited.

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 plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system.

Explanation of symbols

A: Gas barrier laminated film 1: Base film 2: Transparent gas barrier layer 3: Gas barrier coating film 4: Strong adhesion treatment layer 5: Translucent metal thin film layer 11: Plasma CVD apparatus 12: Chamber 13: Supply roller 14: Winding Take-up roller 15: Cooling / electrode drum 16: Auxiliary roller 17: Power supply 18: Vacuum pump 19: Raw material supply nozzle 21: Raw material volatilization supply device 22: Gas supply device 23: Magnet 41: Retractable vacuum deposition device 42: Vacuum chamber 43: Unwinding rolls 44, 45, 51, 52: Guide roll 46: Coating drum 47: Crucible 48: Deposition source 49: Oxygen gas outlet 50: Mask 53: Winding roll

Claims (15)

In a laminated film in which a transparent gas barrier layer is provided on at least one surface of a base film made of polyamide and a gas barrier coating film is further laminated thereon, a strong adhesion is obtained by subjecting the surface of the gas barrier coating film to an easy adhesion treatment. A gas barrier laminate film characterized in that a treatment layer is formed and a semitransparent metal thin film layer is further provided thereon,
The transparent gas barrier layer is a continuous layer containing silicon oxide and a carbon simple substance and / or a carbon compound bonded to a silicon oxide molecular chain in any of graphite, diamond and fullerene, and A gas barrier laminate film, wherein the carbon content decreases from the surface of the transparent gas barrier layer toward the depth direction.   2. The gas barrier laminate film according to claim 1, wherein the easy adhesion treatment is performed by a plasma treatment using a single gas of oxygen, nitrogen, or argon, or a mixed gas thereof.   The gas barrier laminate film according to claim 1 or 2, wherein the semitransparent metal thin film layer is a layer deposited by physical vapor deposition.   The gas-barrier laminated film according to any one of claims 1 to 3, 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 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. The gas barrier laminate film according to any one of claims 1 to 4, which is a gas barrier coating film made of a gas barrier composition obtained by polycondensation of the above with a sol-gel method. The gas barrier laminate film according to claim 5, 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 claim 5 or 6, 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 an ethylene / vinyl alcohol copolymer. 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 5 to 7.   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 It consists of a cured film heat-processed for 10 minutes, The gas-barrier laminated film of any one of Claims 5-8 characterized by the above-mentioned.   The gas barrier according to any one of claims 5 to 9, 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 10, wherein the tertiary amine is N, N-dimethylbenzylamine.   12. The gas barrier laminate film according to claim 5, wherein water in the gas barrier composition is used in a proportion of 0.1 to 100 mol with respect to 1 mol of alkoxide.   The gas barrier laminate film according to any one of claims 5 to 12, wherein the gas barrier composition contains a silane coupling agent. The antistatic coating agent is applied to the opposite side of the surface on which the transparent gas barrier layer of the base film made of polyamide is laminated, and the surface resistivity is 10 ¹² Ω / □ or less. 14. The gas barrier laminate film according to any one of 13 above.   A laminated package using the gas barrier laminated film according to any one of claims 1 to 14.

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