JP2008036948A - Gas-barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas-barrier laminated film whose gas-barrier properties are not deteriorated even when the film is subjected to usual processing as a packaging material. <P>SOLUTION: The gas-barrier laminated film has a substrate layer (1) of a transparent plastic film, a thin aluminum oxide vapor deposition film layer (2) of a thickness of 5-300 nm which is formed on the substrate layer (1), a thin aluminum vapor deposition film layer (3) of 1-5 nm thickness which is formed on the aluminum oxide film layer (2) and the surface of which is subjected to oxygen plasma treatment, and a gas-barrier coat layer (4) with a thickness of 0.02-20 μm which is formed on the aluminum vapor deposition film layer (3) and produced by curing a polymerizable acrylic monomer or a mixture of the monomer and an oligomer. The transmittance of light (which is) 366 nm in wavelength of the two layers of the aluminum oxide vapor deposition film layer (2) and the aluminum vapor deposition film layer (3) is 65-90%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a transparent gas barrier laminate film that is suitably used when high gas barrier properties are required in the fields of packaging of foods, daily necessities, pharmaceuticals, and the like, and fields related to electronic devices.

  Packaging materials used for packaging of food, daily necessities, pharmaceuticals, etc., and packaging materials used for electronic equipment-related materials, etc., to prevent deterioration of the contents and to retain their functions and properties even during packaging In addition, it is necessary to prevent the influence of gases such as oxygen and water vapor that permeate the packaging material, which alters the contents, and it is required to have gas barrier properties that block these gases.

  As packaging materials having ordinary gas barrier properties, vinylidene chloride resin films or films coated with vinylidene chloride resins that are relatively excellent in gas barrier properties have been often used. However, these packaging materials have high gas barrier properties. Cannot be used for packaging that requires Therefore, when a high gas barrier property is required, a packaging material in which a metal foil such as aluminum is laminated as a gas barrier layer has to be used.

  A packaging material in which a metal foil such as aluminum is laminated has almost no influence of temperature and humidity and has a high gas barrier property. However, these packaging materials have many disadvantages, such as being unable to see the contents through them, having to be disposed of as non-combustible materials after use, and being unable to use metal detectors to inspect the contents. Had.

As a packaging material that overcomes these drawbacks, a transparent plastic film substrate layer, a transparent thin film layer of an inorganic oxide such as silicon oxide, aluminum oxide, and magnesium oxide, and an appropriate gas barrier coating layer are provided. A laminated film (Patent Document 1) obtained by laminating is marketed.
Japanese Patent Laid-Open No. 7-164591

  However, the laminated film described in Patent Document 1 deteriorates gas barrier properties such as oxygen permeability and water vapor permeability when subjected to normal processing as a packaging material such as printing, laminating, and bag making. Had the disadvantages.

  The object of the present invention is to provide a particularly high gas barrier property in which the gas barrier property is not deteriorated even if a normal processing as a packaging material is performed in the field of packaging such as foods, daily necessities, and pharmaceuticals, and electronic device-related members. An object of the present invention is to provide a transparent gas barrier laminate film that can be suitably used in the case of manufacturing.

  The gas barrier laminate film of claim 1 of the present invention comprises a base material layer (1) made of a transparent plastic film, and an aluminum oxide vapor deposition thin film layer having a thickness of 5 to 300 nm formed on the base material layer (1). (2), an aluminum vapor deposited thin film layer (3) having a thickness of 1 to 5 nm formed on the aluminum oxide vapor deposited thin film layer (2) and having a surface treated with oxygen plasma, and the aluminum vapor deposited thin film layer (3) A gas barrier coating layer (4) having a thickness of 0.02 to 20 μm formed by curing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer formed thereon, and the aluminum oxide vapor-deposited thin film The light transmittance at a wavelength of 366 nm in the two layers of the layer (2) and the aluminum deposited thin film layer (3) is 65 to 90%.

  The gas barrier laminate film according to claim 2 of the present invention comprises, on a base material layer (1) made of a transparent plastic film, in vacuum, an aluminum oxide deposited thin film layer (2) having a thickness of 5 to 300 nm, and a thickness. After sequentially laminating the 1-5 nm aluminum vapor-deposited thin film layer (3), the surface of the aluminum vapor-deposited thin film layer (3) is subjected to oxygen plasma treatment to form an aluminum oxide vapor-deposited thin film layer (2), an aluminum vapor-deposited thin film layer (3), An uncured flash-deposited coating layer comprising a polymerizable acrylic monomer or a mixture of a monomer and an oligomer is continuously laminated in a vacuum with a light transmittance at a wavelength of 366 nm in the two layers of 65 to 90%. And a gas barrier coating layer (4) having a thickness of 0.02 to 20 μm is formed by irradiating with ultraviolet rays or an electron beam to be cured. .

  Each layer in the gas barrier laminate film of the present invention has the following functions. The aluminum oxide deposited thin film layer (2) having a thickness of 5 to 300 nm is transparent and exhibits excellent gas barrier properties against oxygen, water vapor and the like. The aluminum vapor-deposited thin film layer (3) having a thickness of 1 to 5 nm prevents the water vapor barrier property of the aluminum oxide vapor-deposited thin film layer (2) from deteriorating by performing oxygen plasma treatment on the surface thereof. The transparent gas barrier film layer (4) having a thickness of 0.02 to 20 μm protects the aluminum oxide vapor-deposited thin film layer (2) from external processing such as normal processing such as printing, laminating and bag making, bending and pulling. . Therefore, the gas barrier laminate film of the present invention is transparent and exhibits excellent gas barrier properties against oxygen, water vapor and the like without deterioration of the gas barrier properties even when subjected to normal processing as a packaging material.

  The gas barrier laminate film according to claim 3 of the present invention is characterized in that the polymerizable acrylic monomer or mixture of monomer and oligomer contains monoacrylate, diacrylate and triacrylate.

  As described above, when the polymerizable acrylic monomer or the mixture of the monomer and the oligomer contains monoacrylate, diacrylate and triacrylate, the adhesiveness with the aluminum vapor-deposited thin film layer 3 is good and efficient. An uncured flash-deposited coating layer can be formed, and a gas barrier laminate film with excellent hygiene can be obtained.

  According to a fourth aspect of the present invention, there is provided a gas barrier laminate film, which transmits light having a wavelength of 366 nm in three layers of the aluminum oxide vapor-deposited thin film layer (2), the aluminum vapor-deposited thin film layer (3), and the gas barrier film layer (4). The degree is 70 to 95%.

  In the present invention, the gas barrier coating layer (4) generally has a lower optical refractive index than the aluminum oxide vapor-deposited thin film layer (2) and the aluminum vapor-deposited thin film layer (3) after the oxygen plasma treatment. It is possible to provide a gas barrier laminate film having improved transparency by increasing the light transmittance at a wavelength of 366 nm.

  The gas barrier laminate film according to claim 5 of the present invention is characterized in that the surface of the gas barrier coating layer (4) is subjected to plasma treatment.

  When the surface of the gas barrier coating layer (4) is thus plasma-treated, the adhesion between the gas barrier coating layer 4 and other film layers or printing layers can be improved. A gas barrier laminate film with high hygiene can be provided by removing the cured component.

  According to the present invention, the gas barrier properties are not deteriorated even if normal processing as a packaging material is performed in the field of packaging of foods, daily necessities, pharmaceuticals, etc., and fields related to electronic devices, and the packaging material is seen through. Therefore, it is possible to provide a transparent gas barrier laminate film that can be suitably used when particularly high gas barrier properties are required. Moreover, the gas barrier laminate film of the present invention can be efficiently produced by successively laminating an aluminum oxide deposited thin film layer, an aluminum deposited thin film layer, and a gas barrier coated layer on a base material layer in a vacuum deposition apparatus. Therefore, production costs can be reduced.

  Hereinafter, the best mode for carrying out the gas barrier laminate film of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of a gas barrier laminate film of the present invention. On the base material layer 1, an aluminum oxide vapor-deposited thin film layer 2, an aluminum vapor-deposited thin film layer 3, and a gas barrier coating layer 4 are sequentially laminated in the thickness direction. During this lamination process, the surface of the aluminum vapor-deposited thin film layer 3 is in a state subjected to oxygen plasma treatment.

  In the gas barrier laminate film of the present invention, the base material layer 1 is made of a transparent plastic film. Examples of transparent plastic films include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films, Biodegradable plastic films such as polylactic acid are used.

  These transparent plastic films may be either stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. In particular, polyethylene terephthalate stretched in the biaxial direction is preferably used from the viewpoints of heat resistance and dimensional stability. The transparent plastic film may contain additives such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant. Further, in the transparent plastic film, the surface on the side where other layers are laminated may be subjected to corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion. .

  The thickness of the base material layer 1 made of these transparent plastic films is not particularly limited. However, considering the suitability as a packaging material and the suitability for processing when other layers are laminated, it is practical. Is preferably in the range of 3 to 200 μm, particularly in the range of 6 to 30 μm.

  In the gas barrier laminated film of the present invention, the method for forming the aluminum oxide vapor-deposited thin film layer 2 and the aluminum vapor-deposited thin film layer 3 is not particularly limited, but the aluminum oxide vapor-deposited thin film layer 2 and the aluminum vapor-deposited layer are formed on the surface of the substrate layer 1. In the case where the thin film layer 3 is successively and sequentially laminated in a vacuum, the vacuum deposition method is the best at present.

  In the current vacuum vapor deposition method, the electron source heating method, the resistance heating method, the induction heating method, or the like is preferable as the heating means for the evaporation source material in the vacuum vapor deposition apparatus. Moreover, in order to improve the adhesiveness with the base material layer 1, a plasma assist method, an ion beam assist method, etc. can also be used. Further, in order to increase the transparency of the deposited thin film layer, reactive deposition may be performed by blowing oxygen gas or the like.

  In the gas barrier laminate film of the present invention, the aluminum oxide vapor-deposited thin film layer 2 is transparent and has an excellent gas barrier property that blocks a gas that alters the contents such as oxygen and water vapor.

  The thickness of the aluminum oxide vapor-deposited thin film layer 2 is 5 to 300 nm, more preferably 5 to 100 nm. Here, if the film thickness is less than 5 nm, a uniform vapor-deposited thin film layer may not be obtained, and the function as a gas barrier material cannot be sufficiently achieved. On the other hand, if the film thickness exceeds 300 nm, it is difficult to maintain flexibility in the deposited thin film layer, and if an external stress such as bending or pulling is applied, the deposited thin film layer may be cracked.

  In the gas barrier laminated film of the present invention, the most important role of the aluminum vapor deposited thin film layer 3 is to protect the water vapor barrier property of the aluminum oxide vapor deposited thin film layer 2 from being deteriorated when the gas barrier coated film layer 4 is formed. It is. Next, this protection function will be described in more detail.

  In the gas barrier laminate film of the present invention, the gas barrier coating layer 4 is formed by flash vapor deposition of a polymerizable acrylic monomer or a mixture of a monomer and an oligomer. Here, suppose that the aluminum oxide vapor-deposited thin film layer 2 and the gas barrier coating layer 4 are sequentially laminated in a vacuum without forming the aluminum vapor-deposited thin film layer 3. When these two layers are laminated off-line, there is no problem even if the aluminum vapor deposited thin film layer 3 is not provided. However, when laminating these two layers in-line, the aluminum oxide vapor-deposited thin film layer is affected by the intrusion of the polymerizable acrylic monomer or the monomer and oligomer into the aluminum oxide vapor-deposited thin film layer 2. 2 It is considered that the original excellent water vapor barrier property is inhibited. Therefore, by forming an aluminum vapor-deposited thin film layer 3 having a protective function between the aluminum oxide vapor-deposited thin film layer 2 and the gas barrier coating layer 4, the influence of a polymerizable acrylic monomer or a mixture of monomers and oligomers It is possible to prevent deterioration of the inherent excellent water vapor barrier property of the aluminum oxide vapor-deposited thin film layer 2.

  In the gas barrier laminated film of the present invention, the aluminum vapor-deposited thin film layer 3 has an excellent gas barrier property that blocks the gas that alters the contents such as oxygen and water vapor, like the aluminum oxide vapor-deposited thin film layer 2. However, it is inferior in transparency. For this reason, it is preferable that the thickness of the aluminum vapor-deposited thin film layer 3 is 1 to 5 nm in consideration of a case where it is necessary to confirm the contents by seeing through the gas barrier laminated film. Here, when the film thickness is less than 1 nm, the protective function which is the most important role of the aluminum vapor-deposited thin film layer 3 cannot be sufficiently achieved. On the other hand, if the film thickness exceeds 5 nm, the transparency of the aluminum vapor-deposited thin film layer 3 is inferior, and it is difficult to confirm the contents through the gas barrier laminate film.

  In the gas barrier laminate film of the present invention, oxygen plasma treatment is further performed on the surface of the aluminum vapor-deposited thin film layer 3 in consideration of the need to confirm the contents through the gas barrier laminate film. The aluminum vapor-deposited thin film layer 3 that has been subjected to the oxygen plasma treatment has a light transmittance at a wavelength of 366 nm of 1 to 20%, more preferably 5 to 20%. As a result, the light transmittance at a wavelength of 366 nm in the two layers of the aluminum oxide vapor-deposited thin film layer 2 and the aluminum vapor-deposited thin film layer 3 is 65 to 85%, more preferably 75 to 85%, and the transparency of the gas barrier laminate film is improved. To do.

  The method for plasma-treating the surface of the aluminum vapor-deposited thin film layer 3 is not particularly limited, but contains oxygen atoms such as oxygen, carbon dioxide, and ozone as a gas that exhibits an oxidizing function after being converted into plasma using a DC power source or an RF power source. It is desirable to perform plasma treatment using a mixed gas containing a gas to be used and at least one kind of inert gas such as helium and argon. This is because oxygen plasma is continuously generated stably and the aluminum deposited thin film layer 3 is oxidized from the surface, thereby increasing the light transmittance at a wavelength of 366 nm and improving the transparency of the gas barrier laminate film efficiently. Because it can.

  In the gas barrier laminate film of the present invention, the gas barrier coating layer 4 is an uncured acrylic monomer or a mixture of monomers and oligomers that can be polymerized on the aluminum deposited thin film layer 3 by flash deposition in vacuum. After laminating the flash vapor deposition coating layer, it can be formed by irradiating and curing with ultraviolet rays or electron beams. Therefore, the aluminum oxide vapor-deposited thin film layer 2, the aluminum vapor-deposited thin film layer 3, and the gas barrier coating layer 4 can be sequentially laminated on the base material layer 1 in vacuum in a vacuum vapor deposition apparatus. The production cost can be reduced.

  The uncured flash-deposited coating layer is vaporized by dropping a polymerizable acrylic monomer or a mixture of monomer and oligomer from a nozzle inserted in a high-temperature evaporation source in a vacuum deposition apparatus. Vapor deposition) and the aluminum vapor deposition thin film layer 3 can be continuously laminated.

  When the uncured flash-deposited coating layer is cured by irradiation with ultraviolet rays, a photopolymerization initiator is mixed with a polymerizable acrylic monomer or a mixture of a monomer and an oligomer. Specific examples of the photopolymerization initiator include benzoin ethers, benzophenones, xanthones, and acetophenone derivatives. These photopolymerization initiators are mixed in a proportion of 0.01 to 10% by weight, preferably 0.1 to 2% by weight.

  When the uncured flash vapor deposition coating layer is cured by irradiation with an electron beam, the balance between the thickness of the flash vapor deposition coating layer, the energy condition of the electron beam, the processing speed, and the charge removal becomes important. This is because if excessive electron beam energy is supplied, the flash vapor deposition coating layer is charged, and as a result, the gas barrier properties of the aluminum oxide vapor deposition thin film layer 2 and the aluminum vapor deposition thin film layer 3 may be impaired by peeling discharge. It is.

  The role of the gas barrier coating layer 4 in the gas barrier laminated film of the present invention is that the aluminum oxide vapor-deposited thin film layer 2 and the aluminum vapor-deposited thin film layer 3 have excellent gas barrier properties. This is a protective function in the case of applying, and a protective function in the case where external stress such as bending or pulling is applied. The thickness of the gas barrier coating layer 4 is preferably 0.02 to 20 μm. Since the gas barrier coating layer 4 generally has a light refractive index smaller than that of the aluminum oxide vapor deposition thin film layer 2 and the aluminum vapor deposition thin film layer 3 after the oxygen plasma treatment, a light beam having a wavelength of 366 nm is obtained by laminating the gas barrier coating layer 4. It also has a function of increasing the transmittance by 1 to 15%. The degree of the increase in light transmittance also depends on the thickness of the gas barrier coating layer 4 and the light refractive index of the aluminum vapor deposited thin film layer 3 after the oxygen plasma treatment. Here, when the film thickness is less than 0.02 μm, it is difficult to form a uniform coating layer. On the other hand, if the film thickness exceeds 20 μm, it is difficult to sufficiently cure the coating layer, and these protective functions cannot be exhibited. And by controlling the film thickness of the gas barrier laminate film 4 in the range of 0.02 to 20 μm, the light transmittance at a wavelength of 366 nm is 70 to 95%, more preferably 80 to 95%, and higher transparency. Can be obtained.

  In the gas barrier laminate film of the present invention, the polymerizable acrylic monomer or mixture of monomer and oligomer, which is a raw material for the gas barrier coating layer 4, contains at least one of monoacrylate, diacrylate and triacrylate. It is preferable. As these acrylates, polyester monomers, polyether acrylates, acrylic acrylates, urethane acrylates, epoxy acrylates, silicone acrylates, polyacetal acrylates, polybutadiene acrylates, melamine acrylates and other highly polymerizable acrylic monomers or oligomers are appropriately selected. Can be used.

  Moreover, when 1 or more types of monoacrylates provided with a functional group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and a phenyl group are used, the adhesion to the aluminum deposited thin film layer 3 can be improved. That is, diacrylate is used as a basic component, and triacrylate is used to improve the degree of cross-linking, but these alone do not provide good adhesion to the aluminum vapor-deposited thin film layer 3. Is preferably used.

  There are various types of monoacrylates, diacrylates and triacrylates, which are not particularly limited, but have good adhesion to the aluminum vapor deposited thin film layer 3 and can efficiently form an uncured flash vapor deposited thin film layer. It is preferable to select one having excellent hygiene. Specific examples of the monoacrylate include 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-succinic acid, methoxy-polyethylene glycol acrylate, and phenoxy-polyethylene glycol acrylate. Examples of the diacrylate include triethylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, and 1,9-nonanediol diacrylate. Examples of the triacrylate include trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. These ratios are desirably set to, for example, monoacrylate / diacrylate / triacrylate = 10/70/20 (% by weight).

  The viscosity of the polymerizable acrylic monomer or the mixture of the monomer and the oligomer is preferably 200 mPa · s / 25 ° C. or less, more preferably 100 mPa · s / 25 ° C. or less. This is done by dropping a polymerizable acrylic monomer or a mixture of a monomer and an oligomer from a nozzle inserted in a high-temperature evaporation source in a vacuum vapor deposition apparatus and vaporizing it instantaneously to deposit aluminum. When the uncured flash vapor deposition coating layer is continuously laminated on the surface of the thin film layer 3 and its viscosity is too high, it can be dropped little by little at a constant rate from a nozzle inserted into a high temperature evaporation source. This is because it becomes difficult.

  Since the gas barrier laminate film of the present invention is used as a packaging material in the fields of packaging such as foods, daily necessities, and pharmaceuticals and electronic equipment-related members, a polymerizable acrylic monomer or a mixture of monomers and oligomers is The PII (Primary Irritation Index) is preferably 2.0 or less. In addition, PII shows the degree of skin disorder of chemicals, and the smaller the value, the lower the irritation.

  In the gas barrier laminate film of the present invention, the surface of the gas barrier coating layer 4 is preferably subjected to plasma treatment. This is because the uncured component of a polymerizable acrylic monomer or a mixture of a monomer and an oligomer used as a raw material of the gas barrier coating layer 4 when used as a packaging material in the packaging field of foods, daily necessities, pharmaceuticals and the like. It is for removing and improving the hardening degree to cope with problems such as food hygiene. Moreover, in order to improve the adhesion between the gas barrier coating layer 4 and other film layers or printing layers when laminating other film layers or printing layers on the gas barrier coating layer 4 of the gas barrier laminate film. It is.

  When the gas barrier coating layer 4 is subjected to plasma treatment, plasma is continuously generated stably using a DC power source or an RF power source, and an uncured component of a polymerizable acrylic monomer or a mixture of a monomer and an oligomer In order to efficiently remove hydrogen, it is necessary to use a mixed gas for plasma treatment containing a normal gas such as hydrogen, oxygen, nitrogen, carbon dioxide and at least one inert gas such as helium or argon. desirable.

  The gas barrier laminate film of the present invention is not limited as long as at least the aluminum oxide vapor-deposited thin film layer 2, the aluminum vapor-deposited thin film layer 3, and the gas barrier coat layer 4 are sequentially laminated on the base material layer 1, and a more complicated laminate. You may take the structure. For example, the aluminum oxide vapor-deposited thin film layer 2, the aluminum vapor-deposited thin film layer 3, and the gas barrier coating layer 4 may be sequentially laminated on both sides of the base material layer 1, respectively. Moreover, on the laminated body of the aluminum oxide vapor deposition thin film layer 2, the aluminum vapor deposition thin film layer 3, and the gas barrier film layer 4, the laminated body of the aluminum oxide vapor deposition thin film layer 2, the aluminum vapor deposition thin film layer 3, and the gas barrier film layer 4 May be laminated in a double layer. Furthermore, a printing layer may be laminated on the surface of the gas barrier coating layer 4. In this case, a printing layer having a thickness of 0.1 to 2.0 μm can be laminated without any particular limitation by a known printing method or coating method using a conventional printing ink conventionally used.

  The gas barrier laminate film of the present invention can be laminated with other films and used as a packaging material in the fields of packaging such as foods, daily necessities, and pharmaceuticals, and electronic device related members. For example, the gas barrier laminate film of the present invention may be used as the outermost layer, and an intermediate film layer, a heat seal layer, or the like may be laminated on the inner surface (gas barrier coat layer 4) side with an adhesive. Further, the gas barrier laminate film of the present invention is used as an intermediate layer, an outer film layer or the like is laminated on the outer surface (base material layer 1) side through an adhesive, and the inner surface (gas barrier coating layer 4) side. You may make it the structure which laminated | stacked the heat seal layer etc. through the adhesive agent.

  A transparent film layer is used as the intermediate film layer or the outer film layer. Examples of such transparent film layers include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films, polycarbonate films, polyacrylonitrile films, and polyimide films. It is done. Examples of the heat seal layer include polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid ester copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester. Synthetic resins such as copolymers and cross-linked products of these metals are used. Although the thickness of an intermediate | middle film layer, an outer film layer, and a heat seal layer is decided according to the objective, generally it is the range of 15-200 micrometers. As the adhesive, a one-component curable type or two-component curable polyurethane adhesive or the like is used. In order to laminate these layers through an adhesive, a dry laminating method or the like can be used. Further, as another method for laminating the heat seal layer, a method (extrusion lamination) of hot-melt extrusion of the synthetic resin of the heat seal layer can be used.

  In the following Examples 1 and 2, as shown in FIG. 1, an aluminum oxide vapor-deposited thin film layer 2, an aluminum vapor-deposited thin film layer 3 (the surface is subjected to oxygen plasma treatment) and a gas barrier property on the base material layer 1. A gas barrier laminate film of the present invention in which the coating layer 4 was sequentially laminated was produced.

<Example 1>
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was prepared as the base material layer 1 and placed in a vacuum deposition apparatus. Metal aluminum was evaporated by an electron beam heating method, oxygen gas was introduced, and an aluminum oxide vapor deposition thin film layer 2 having a thickness of 15 nm was laminated on the base material layer 1. Continuously, metal aluminum was evaporated by an electron beam heating method, and an aluminum deposited thin film layer 3 having a thickness of 3 nm was laminated on the aluminum oxide deposited thin film layer 2. Using an RF power source, a 1/1 mixed gas of oxygen and argon was turned into plasma, and the surface of the aluminum deposited thin film layer 3 was subjected to oxygen plasma treatment. Continuously, 10/70/20 (weight) of 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate on the aluminum deposited thin film layer 3 by flash deposition. %)), An uncured flash-deposited coating layer having a thickness of 0.2 μm was laminated. The flash vapor-deposited coating layer was irradiated with an electron beam and cured to form a gas barrier coating layer 4. Thus, the gas barrier laminate film of Example 1 was produced.

<Example 2>
In the same manner as in Example 1, an aluminum oxide vapor-deposited thin film layer 2, an aluminum vapor-deposited thin film layer 3 and a gas barrier coating layer 4 were sequentially laminated on the base material layer 1, and then a 1 / One mixed gas was turned into plasma, and the surface of the gas barrier coating layer 4 was subjected to plasma treatment. Thus, a gas barrier laminate film of Example 2 was produced.

<Comparative Example 1>
After the aluminum oxide vapor-deposited thin film layer 2 and the aluminum vapor-deposited thin film layer 3 were sequentially laminated on the base material layer 1, the gas barrier coating layer 4 was laminated without subjecting the surface of the aluminum vapor-deposited thin film layer 3 to oxygen plasma treatment. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 1 was produced.

<Comparative example 2>
After the aluminum oxide vapor deposition thin film layer 2 was laminated on the base material layer 1, the gas barrier coating layer 4 was laminated without laminating the aluminum vapor deposition thin film layer (without performing oxygen plasma treatment). Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 2 was produced.

  Hereinafter, the gas barrier laminate films of Examples 1 and 2 and Comparative Examples 1 and 2 produced as described above are referred to as a single film.

  Next, a printing layer having a thickness of 1.2 μm was laminated on the surface of the gas barrier coating layer 4 of each of the single films of Examples 1 and 2 and Comparative Examples 1 and 2. Hereinafter, these are called printing films.

Next, a heat seal layer of polypropylene having a thickness of 50 μm was laminated on the surface of the print layer of each of the print films of Examples 1 and 2 and Comparative Examples 1 and 2 via a polyurethane adhesive of 5 g / m ² . . Hereinafter, these are called laminated films.

<Evaluation>
1. Light transmittance A single film of the gas barrier laminate film of Examples 1 and 2 and Comparative Examples 1 and 2 was prepared. In Examples 1 and 2, an aluminum oxide vapor-deposited thin film layer 2 and an aluminum vapor-deposited thin film layer 3 after oxygen plasma treatment were used. Three layers with a gas barrier coating layer 4, in Comparative Example 1, three layers of an aluminum oxide deposited thin film layer 2, an aluminum deposited thin film layer 3, and a gas barrier coated layer 4, and in Comparative Example 2, an aluminum oxide deposited thin film layer 2 and a gas barrier property. The light transmittance (%) at a wavelength of 366 nm in two layers with the coating layer 4 was measured.

  Separately, in Examples 1 and 2, two layers of an aluminum oxide vapor-deposited thin film layer 2 and an aluminum vapor-deposited thin film layer 3 after oxygen plasma treatment were used, and in Comparative Example 1, an aluminum oxide vapor-deposited thin film layer 2 and an aluminum vapor-deposited thin film layer 3 The light transmittance (%) at a wavelength of 366 nm in the two layers was measured.

2. Oxygen transmission rate For the single films of Examples 1 and 2 and Comparative Examples 1 and 2, oxygen in a 30 ° C.-70% RH atmosphere was measured with an oxygen transmission meter (MOCON OX-TRAN 2/21) manufactured by Modern Control. The permeability (cc / m ² · 24 h · MPa) was measured.

3. Water Vapor Permeability For single films, printed films and laminated films of Examples 1 and 2 and Comparative Examples 1 and 2, 40 ° C.-90 was measured with a water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control. The water vapor permeability (g / m ² · 24 h) in an atmosphere of% RH was measured.

4). Lamination strength The laminate strength (N / 15 mm) of the test pieces slit to a width of 15 mm from the laminated films of Examples 1 and 2 and Comparative Examples 1 and 2 was measured with an ordinary Tensilon universal testing machine.
These measurement results are shown in Table 1.

  As can be seen from Table 1, the gas barrier laminate films (single film, print film and laminate film) of Example 1 and Example 2 have high light transmittance, low oxygen permeability and water vapor permeability, and high laminate strength. Have both. In particular, the laminated film of Example 2 had a high laminate strength.

  On the other hand, the gas barrier laminate film of Comparative Example 1 in which the surface of the aluminum vapor deposited thin film layer 3 was not subjected to oxygen plasma treatment was inferior in transparency as compared with the gas barrier laminate films of Example 1 and Example 2.

  Further, the gas barrier laminated film (single film, printed film, and laminated film) of Comparative Example 2 having no aluminum vapor deposited thin film layer was remarkably high in water vapor permeability and inferior in gas barrier properties.

It is sectional drawing of the gas barrier laminated film in the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Aluminum oxide vapor deposition thin film layer 3 ... Aluminum vapor deposition thin film layer 4 ... Gas barrier property coating layer

Claims (5)

A base material layer (1) made of a transparent plastic film;
An aluminum oxide deposited thin film layer (2) having a thickness of 5 to 300 nm formed on the substrate layer (1);
An aluminum vapor deposited thin film layer (3) having a thickness of 1 to 5 nm formed on the aluminum oxide vapor deposited thin film layer (2) and having a surface subjected to oxygen plasma treatment;
A gas barrier coating layer (4) having a thickness of 0.02 to 20 μm formed by curing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer formed on the aluminum vapor-deposited thin film layer (3); Have
A gas barrier laminate film, wherein light transmittance at a wavelength of 366 nm in the two layers of the aluminum oxide vapor-deposited thin film layer (2) and the aluminum vapor-deposited thin film layer (3) is 65 to 90%.   On a base material layer (1) made of a transparent plastic film, an aluminum oxide vapor-deposited thin film layer (2) having a thickness of 5 to 300 nm and an aluminum vapor-deposited thin film layer (3) having a thickness of 1 to 5 nm are formed in a vacuum. After sequentially laminating, the surface of the aluminum vapor-deposited thin film layer (3) was subjected to oxygen plasma treatment, and the light transmittance at a wavelength of 366 nm in the two layers of the aluminum oxide vapor-deposited thin film layer (2) and the aluminum vapor-deposited thin film layer (3) was 65 to 65. 90%, and continuously in vacuum, an uncured flash vapor-deposited coating layer composed of a polymerizable acrylic monomer or a mixture of a monomer and an oligomer is laminated, and cured by irradiation with ultraviolet rays or electron beams. A gas barrier laminate film, wherein a gas barrier coating layer (4) having a thickness of 0.02 to 20 μm is formed.   The gas barrier laminate film according to claim 1 or 2, wherein the polymerizable acrylic monomer or a mixture of a monomer and an oligomer contains monoacrylate, diacrylate and triacrylate.   The light transmittance at a wavelength of 366 nm in the three layers of the aluminum oxide vapor-deposited thin film layer (2), the aluminum vapor-deposited thin film layer (3) and the gas barrier film layer (4) is 70 to 95%. The gas barrier laminate film according to any one of claims 1 to 3.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the surface of the gas barrier coating layer (4) is subjected to plasma treatment.

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