Gas barrier film and packaging body

Abstract

Provided are: a gas barrier film that includes a vapor deposition layer (B) that includes at least one metal element selected from among zinc, magnesium, and calcium and a compound that has a carbonyl group on a plastic film; and a packaging body that includes the gas barrier film. The peak ratio (A1575 / A1687) of the absorption peak height A1687 at a wavenumber of 1687 cm-1 to the absorption peak height A1575 at a wavenumber of 1575 m-1 on an infrared absorption spectrum for the vapor deposition layer (B) is preferably 0.1–5.0.

Description

Gas barrier film and packaging

[0001] The present invention relates to a gas barrier film having excellent flexibility.

[0002] Packaging materials used for packaging foods, pharmaceuticals, etc. are required to have barrier properties against oxygen and water vapor (hereinafter referred to as gas barrier properties) in order to prevent the contents, flavor, and efficacy from being altered or reduced due to oxidation. Resin films having vapor-deposited films are used because they can provide high barrier performance at low cost. Examples of gas barrier films having vapor-deposited films include a film in which aluminum oxide (AlOx) and / or silicon oxide (SiOx) is vapor-deposited on a polyethylene terephthalate film, or a film in which multiple vapor-deposited silicon oxide films are laminated (see, for example, Patent Document 1), and a gas barrier laminate film in which a vapor-deposited material containing metallic silicon and silicon oxide, and a vapor-deposited material containing a metal or metal oxide selected from aluminum, zinc, tin, and iron are vapor-deposited on a resin substrate having an anchor coat layer (see, for example, Patent Document 2).

[0003] However, metal oxide vapor-deposited films are generally weak against bending, such as twisting and folding, and cracks can easily occur in parts of the vapor-deposited film when laminating it with other films or when bending it during bag making after lamination, resulting in a decrease in barrier performance.

[0004] JP 2013-253319 A JP 2014-069389 A

[0005] An object of the present invention is to provide a gas barrier film that has excellent flexibility without cracking in parts of the vapor-deposited film and has good gas barrier properties, particularly at high humidity.

[0006] That is, the present invention provides a gas barrier film having, on a plastic film, a vapor-deposited layer (B) containing at least one metal element selected from the group consisting of zinc, magnesium, and calcium, and a compound having a carbonyl group.

[0007] The present invention also provides a package containing the gas barrier film described above.

[0008] According to the present invention, it is possible to provide a gas barrier film which has excellent flexibility without cracking in parts of the vapor-deposited film and has gas barrier properties particularly at high humidity, and a package using the same.

[0009] (Definition of Terms) In this specification, "~" means greater than or equal to the value before "~" and less than or equal to the value after "~".

[0010] (Gas Barrier Film) The gas barrier film of the present invention is characterized in that it has a vapor-deposited layer (B) on a plastic film, the vapor-deposited layer (B) containing at least one metal element selected from the group consisting of zinc, magnesium, and calcium, and a compound having a carbonyl group.

[0011] (Plastic Film) The material of the plastic film serving as the substrate used in the present invention is not particularly limited, and it is possible to use plastic films that are used as packaging materials for packaging foods, medicines, etc. Specific examples include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, nylon film, polyacrylonitrile film, polyolefin films such as polyethylene films (OPE: biaxially oriented polyethylene film, LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film) and polypropylene films (CPP: non-oriented polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, cellophane, etc.

[0012] When mono-material packaging is considered, a film made of a thermoplastic resin containing an olefin resin as a main component can be used as the substrate. Specific examples of olefin resins include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, ethylene-propylene copolymers, α-olefin polymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl acrylate copolymers, cyclic olefin resins, ionomer resins, and polymethylpentene; and modified olefin resins obtained by modifying olefin resins with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids.

[0013] It is also preferable to use a film made of a material containing biomass-derived components. Biomass films are commercially available from various companies, and for example, sheets such as those listed in the list of biomass-certified products listed by the Japan Organics Recycling Association can be used.

[0014] Specifically, well-known films are made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0015] Alternatively, products using biomass raw materials classified by the biomass plastic content specified in ISO 16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 1012 particles, and this rate is the same for atmospheric carbon dioxide, so this rate remains the same even in plants that fix this carbon dioxide through photosynthesis. Therefore, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin using an accelerator mass spectrometer, the plant-derived resin content in the resin, i.e., the biomass plastic content, can be determined. Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO 16620 or ASTM D6866, include products manufactured by Braskem under the trade names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films using these as raw materials can be suitably used.

[0016] For example, biomass polyolefin films, such as biomass polyethylene films and biomass polyethylene-polypropylene films, containing polyethylene resins made from biomass-derived ethylene glycol are known as alternatives to conventional polyolefin films made from petroleum-based raw materials. The polyethylene resin is not particularly limited except that biomass-derived ethylene glycol is used as part of the raw material. Examples of the polyethylene resin include ethylene homopolymers and copolymers of ethylene and α-olefins containing ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units). These can be used alone or in combination of two or more. The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples include α-olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins, such as low-density polyethylene resins, medium-density polyethylene resins, and linear low-density polyethylene resins, can be used. Among them, from the viewpoint of making it more difficult for damage such as holes or tears to occur even when films are rubbed against each other, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred, and a density of 0.910 to 0.925 g / cm ３ More preferred is a linear low density polyethylene resin in which

[0017] The biomass film may be a laminate of multiple biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film.

[0018] The plastic film may be subjected to some surface treatment, such as a physical treatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, or flame treatment, or a chemical treatment such as oxidation treatment using chemicals, in order to enhance the adhesion of the vapor-deposited layer (B) or vapor-deposited layer (A) described below. Alternatively, the plastic film may have a coating layer, such as an anchor coating agent, that enhances adhesion.

[0019] The plastic film can be produced from the above-mentioned resin by a conventionally known film-forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc. The film may be an unstretched film, or may be one that has been stretched uniaxially or biaxially using a tenter method, a tubular method, etc., from the viewpoint of the strength, dimensional stability, and heat resistance of the film (1).

[0020] The plastic film may contain additives as needed. Specifically, plastic compounding agents and additives such as elastomers, lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, and pigments may be added to improve or modify processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, mildew resistance, electrical properties, strength, etc. The amount of additive added is adjusted within a range that does not affect other properties or recyclability.

[0021] The thickness of the plastic film is not particularly limited and may be appropriately selected from the range of 0.1 to 300 μm in terms of formability and transparency. It is preferably in the range of 0.3 to 100 μm. If the thickness is less than 0.1 μm, the strength may be insufficient, and if it exceeds 300 μm, the rigidity may be too high, making processing difficult.

[0022] From the viewpoint of recycling, it is preferable that the layer structure is as simple as possible, but from the viewpoint of distribution of the packaging material, printing is often required to indicate the contents of the packaging material or a description or name of the product. The plastic film used as the base material is also often printed.

[0023] (Printed Layer) The printed layer is a layer on which characters, figures, symbols, and other desired designs are printed. The printing method and printing ink are not particularly limited, and known printing methods and printing inks can be used. Printing inks using methods such as gravure printing, flexographic printing, lithographic offset printing, and inkjet recording printing are often used for the film used as the substrate. Printing inks that combine these printing methods with methods of curing using active energy rays such as ultraviolet (UV), LED, and electron beam (EB), or methods of curing using heat, are also used. Depending on the solvent used, inks may be referred to as aqueous inks or organic solvent-based inks.

[0024] Specific examples include gravure printing ink and flexographic printing ink (in some industries, gravure printing ink and flexographic printing ink are sometimes referred to as liquid ink), ultraviolet-curable ink for lithographic offset printing, electron-beam-curable ink for lithographic offset printing, ultraviolet-curable ink for inkjet recording and printing, and electron-beam-curable ink for inkjet recording and printing.

[0025] The position where the printed layer printed using these inks is provided is arbitrary, and it may be provided on the first substrate, or a substrate on which a separate printed layer is provided may be one of the constituent components of the laminate of the present invention, and the position is arbitrary. Furthermore, the ink may contain a resin, a colorant, and a solvent as essential components, or it may be a so-called clear ink that contains a resin and a solvent but does not substantially contain a colorant. Below, we will explain the liquid inks that are most commonly used for printing on films.

[0026] The resin used in the liquid ink is not particularly limited and may include, for example, acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc., and one or more of these may be used in combination. Preferably, at least one or two or more selected from polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, and cellulose-based resin are used.

[0027] Colorants used in liquid inks include inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite; organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments; and extender pigments such as calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.

[0028] Liquid inks for film printing are often organic solvent-based inks. The organic solvent used preferably does not contain an aromatic hydrocarbon organic solvent. More specific examples include alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, and n-octane; and alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane. These may be used alone or in combination of two or more.

[0029] (Vapor-deposited layer (A) of aluminum oxide and / or silicon oxide) On the plastic film, an aluminum oxide (also called aluminum oxide, alumina, or AlOx, and examples thereof include AlO and Al ２ O ３ and / or silicon oxide (sometimes called silicon oxide, silica, or SiOx, and is not limited to SiO or SiO ２ The plastic film may have a vapor-deposited layer (A) of various silicon oxides such as silicon dioxide, silicon dioxide, silicon dioxide powder ...

[0030] The vapor-deposited layer (A) is preferably formed by a vapor-phase thin-film formation method. Vapor-phase thin-film formation methods used to form the vapor-deposited layer (A) in the present invention include physical deposition methods (hereinafter referred to as PVD methods) such as vacuum deposition, sputtering, and ion plating, and chemical deposition methods (hereinafter referred to as CVD methods). Any method may be used as long as the effects of the present invention can be obtained. As described above, the vapor-phase thin-film formation method used in the present invention is not particularly limited, but PVD methods such as vacuum deposition, sputtering, and ion plating are preferred because they allow for the easy formation of stable thin films, and it is most preferred to form the thin film by vacuum deposition.

[0031] The vapor deposition process used as the PVD method involves heating a target such as a metal, metal oxide, metal hydroxide, or resin (hereinafter, these vapor deposition raw materials may be collectively referred to as the target) with various heat sources to evaporate it, and then depositing it as an amorphous or crystalline film on the surface of a substrate maintained at a lower temperature. This method can be used either as a batch method in which the entire processing surface is processed at once, or as a method in which the substrate or reaction tank is moved to continuously process equipment or different processing surfaces.

[0032] The vapor deposition process of the present invention can be carried out under pressurized, normal pressure, reduced pressure, vacuum, and its swing, in air, or in an inert gas atmosphere. By carrying out the process under reduced pressure or vacuum, it is possible to improve the evaporation rate and lower the evaporation temperature, and by applying pressure, it is possible to promote the deposition of the evaporated material. Furthermore, by using a vacuum or inert atmosphere, it is possible to control the oxidation of the metal, metal oxide, metal hydroxide, etc., and the support. Furthermore, if oxidation during the vapor deposition process can be controlled or tolerated, it is also possible to carry out the process in an air atmosphere, taking cost into consideration.

[0033] In the present invention, a desirable thin film can be obtained depending on the purpose by adjusting the deposition conditions. The conditions include the pressure in the chamber and the contact time between the target vapor, the molecules present in the atmosphere, and the substrate surface in order to control the chemical structure of the target vapor. By controlling this time, the composition of the deposited thin film can be controlled. Furthermore, the structure of the thin film surface can be controlled by contacting the thin film with oxygen or water vapor after deposition.

[0034] Controlling the chemical structure of the target deposition material means, for example, adding water vapor or oxygen during deposition to obtain a compound in which a hydroxyl group or oxygen is added to the target metal as a deposition layer, and deposition conditions can be appropriately considered depending on the desired deposition film.

[0035] The sputtering method in the present invention is not particularly limited as long as the effects of the present invention can be obtained, and can be selected from DC sputtering, RF sputtering, magnetron sputtering, ion beam sputtering, RF magnetron sputtering, etc., but magnetron sputtering and RF magnetron sputtering are preferred because they allow highly efficient sputtering. －４It is desirable to carry out the process in a processing space such as a chamber that is decompressed to 0.2 Pa or less and into which an inert gas (e.g., argon) has been introduced. In the processing space, a target serving as the raw material for the thin film and a substrate are placed facing each other. A permanent magnet and, if necessary, a holder or other device for holding the target are placed behind the target.

[0036] The magnetic field of the permanent magnet can constrain the spiral trajectory of electrons present in the processing space, generating a high-density plasma region. The presence of the high-density plasma region promotes ionization of the inert gas, and the ions collide with the target, generating target microparticles, which then adhere to the substrate, forming a thin film.

[0037] The RF output during RF magnetron sputtering is not particularly limited and may be adjusted to achieve an appropriate film formation rate. The temperature of the substrate during film formation is preferably controlled to be between room temperature and approximately 100°C.

[0038] The thickness of the vapor-deposited layer (A) is preferably 10 nm or more and 500 nm or less as the thickness of the layer at which gas barrier properties are exhibited. If the layer thickness is thinner than 10 nm, there may be areas where sufficient gas barrier properties are not ensured, and problems such as variations in gas barrier properties within the substrate surface may occur. If the layer thickness is thicker than 500 nm, the residual stress within the vapor-deposited layer (A) may increase, causing cracks in the vapor-deposited layer (A) under high-temperature and high-humidity environments, resulting in problems of reduced gas barrier properties. From the viewpoint of ensuring flexibility, the lower limit is more preferably 20 nm or more and the upper limit is more preferably 300 nm or less. The thickness of the vapor-deposited layer (A) can usually be measured by cross-sectional observation using a transmission electron microscope (TEM).

[0039] The vapor-deposited layer (A) may be a mixture of aluminum oxide and silicon oxide. Among these, a composite oxide of aluminum oxide and silicon oxide is more preferred. That is, in this composite oxide, the mixing ratio of aluminum oxide and silicon oxide is preferably 20% by mass or more and 70% by mass or less of Al (aluminum) in terms of the mass ratio of metal atoms, i.e., the mass ratio of metal atoms. When it is 20% by mass or more, excellent gas barrier properties are achieved. When it is 70% by mass or less, excessive hardness of the vapor-deposited layer (A) can be prevented.

[0040] (Vapor-deposited layer (B)) The gas barrier film of the present invention is characterized by having a vapor-deposited layer (B) containing at least one metal element and a compound having a carbonyl group. The vapor-deposited layer (B) is preferably formed by a vapor-phase thin film formation method, similar to the vapor-deposited layer (A).

[0041] The vapor deposition layer (B) is preferably formed by a vapor phase thin film formation method. Vapor phase thin film formation methods used to form the vapor deposition layer (B) in the present invention include physical deposition methods (hereinafter referred to as PVD methods) such as vacuum deposition, sputtering, and ion plating, and chemical deposition methods (hereinafter referred to as CVD methods). Any method may be used as long as the effects of the present invention can be obtained. As described above, the vapor phase thin film formation method used in the present invention is not particularly limited, but PVD methods such as vacuum deposition, sputtering, and ion plating are preferred because they allow for the easy formation of stable thin films, and it is most preferred to form the thin film by vacuum deposition.

[0042] The vapor deposition process used as the PVD method involves heating a target, such as a metal, metal oxide, metal hydroxide, carbonyl group-containing compound, or metal ion-containing carbonyl group-containing compound (hereinafter, these vapor deposition raw materials may be collectively referred to as the target), with various heat sources to evaporate it, and depositing it as an amorphous or crystalline film on the surface of a substrate maintained at a lower temperature. This method can be used either as a batch method in which the entire processing surface is processed at once, or as a method in which the substrate or reaction tank is moved to continuously process equipment or different processing surfaces.

[0043] The metal element contained in the vapor-deposited layer (B) is preferably at least one metal element selected from the group consisting of zinc, magnesium, and calcium, more preferably at least one selected from zinc and magnesium, and particularly preferably zinc. Specifically, a metal compound containing one of these metal elements is used as the target. Examples of metal compounds include metals such as zinc, magnesium, and calcium; metal oxides such as zinc oxide, magnesium oxide, and calcium oxide; metal hydroxides such as zinc hydroxide, magnesium hydroxide, and calcium hydroxide; and metal ion-containing carbonyl group-containing compounds such as zinc acrylate, zinc terephthalate, magnesium acrylate, magnesium terephthalate, calcium acrylate, and calcium terephthalate. These metal compounds may be used alone or in combination.

[0044] Examples of the compound having a carbonyl group contained in the vapor deposition layer (B) and / or used in the target include terephthalic acid, pyromellitic acid, citric acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azalic acid, sebacic acid, phthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, 4,4′-dibenzoic acid, 2-chloroterephthalic acid, ... Phthalic acid, 4,4'-oxybisbenzoic acid, 4,5-dichlorophthalic acid, 3-ethyl-3-methylglutaric acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, isocinchomeronic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, tetrafluoroterephthalic acid, 4,4' -carbonyldibenzoic acid, 3-oxoglutaric acid, 4,4'-methylenedibenzoic acid, 2-methylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, trimesic acid, [1,1'-biphenyl]-3,4',5-tricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, hemimellitic acid, 1,3,5-pentanetricarboxylic acid, tricarballylic acid, trimellitic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,3',4,4'- Preferred are polycarboxylic acids such as biphenyltetracarboxylic acid, biphenyl-3,3',5,5'-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid, and unsaturated carboxylic acid monomers such as acrylic acid, 4-[[6-(acryloyloxy)hexyl]oxy]benzoic acid, and 2-fluoroacrylic acid, with terephthalic acid, pyromellitic acid, acrylic acid, citric acid, phthalic acid, isophthalic acid, trimellitic acid, and 4,4'-dibenzoic acid being particularly preferred. These carbonyl group-containing compounds may be used alone or in combination of two or more.

[0045] The thickness of the vapor-deposited layer (B) is not particularly limited as long as the effects of the present invention are obtained. As described above, the thickness of the vapor-deposited layer (B) is not particularly limited, but is preferably 1 to 200 nm, more preferably 3 to 150 nm, and particularly preferably 5 to 100 nm.

[0046] The ratio of the metal element to the compound having a carbonyl group in the vapor-deposited layer (B), converted into the molar ratio of the metal compound to the compound having a carbonyl group, is preferably in the range of 1:10,000 to 10,000: 1, more preferably in the range of 1:100 to 100: 1, and particularly preferably in the range of 1:10 to 10: 1. Within this range, the oxygen barrier property is excellent.

[0047] In the present invention, the target is preferably a mixture of a metal compound such as a metal, metal oxide, or metal hydroxide with a carbonyl group-containing compound, and a mixture of a metal and a carbonyl group-containing compound is preferred. By simultaneously depositing the metal compound and the carbonyl group-containing compound using the mixture, a deposited layer in which the carbonyl group-containing compound is ionically crosslinked can be obtained in the deposited layer (B). The mixing ratio of the metal compound to the carbonyl group-containing compound, converted into a molar ratio, is preferably in the range of 1:10,000 to 10,000:1, more preferably in the range of 1:100 to 100:1, and particularly preferably in the range of 1:10 to 10:1.

[0048] In the present invention, it is preferable to use separate targets, one for a metal compound such as a metal, metal oxide, or metal hydroxide, and the other for a carbonyl group-containing compound. Separating the targets between the metal compound and the carbonyl group-containing compound makes it possible to control the deposition amount of each. Simultaneous deposition of the metal compound and the carbonyl group-containing compound allows for the formation of a deposition layer (B) in which the carbonyl group-containing compound is ionically crosslinked. The deposition amounts of each, converted into the molar ratio of the metal compound to the carbonyl group-containing compound, are preferably in the range of 1:10,000 to 10,000:1, more preferably 1:100 to 100:1, and particularly preferably 1:10 to 10:1.

[0049] In the present invention, it is preferable to use a metal ion-containing carbonyl group-containing compound as the target. This can increase the concentration of ionic crosslinking of carbonyl groups by metal ions in the vapor deposition layer (B). Among these, zinc acrylate and zinc terephthalate are preferably used as the metal ion-containing carbonyl group-containing compound.

[0050] The vapor deposition process of the present invention can be carried out under pressurized, normal pressure, reduced pressure, vacuum, and its swing, in air, or in an inert gas atmosphere. By carrying out the process under reduced pressure or vacuum, it is possible to improve the evaporation rate and lower the evaporation temperature, and by applying pressure, it is possible to promote the deposition of the evaporated material. Furthermore, by using a vacuum or inert atmosphere, it is possible to control the oxidation of the metal, metal oxide, metal hydroxide, etc., and the support. Furthermore, if oxidation during the vapor deposition process can be controlled or tolerated, it is also possible to carry out the process in an air atmosphere, taking cost into consideration.

[0051] In the present invention, a desirable thin film can be obtained depending on the purpose by adjusting the deposition conditions. The conditions include the pressure in the chamber and the contact time between the target vapor, the molecules present in the atmosphere, and the substrate surface in order to control the chemical structure of the target vapor. By controlling this time, the composition of the deposited thin film can be controlled. Furthermore, the structure of the thin film surface can be controlled by contacting the thin film with oxygen or water vapor after deposition.

[0052] Controlling the chemical structure of the target deposition material means, for example, adding water vapor or oxygen during deposition to obtain a compound in which a metal ion and a carbonyl group are ionically crosslinked as a deposition layer, and deposition conditions can be appropriately determined depending on the desired deposition film.

[0053] The sputtering method in the present invention is not particularly limited as long as the effects of the present invention can be obtained, and can be selected from DC sputtering, RF sputtering, magnetron sputtering, ion beam sputtering, RF magnetron sputtering, etc., but magnetron sputtering and RF magnetron sputtering are preferred because they allow highly efficient sputtering. －４ It is desirable to carry out the process in a processing space such as a chamber that is decompressed to 0.2 Pa or less and into which an inert gas (e.g., argon) has been introduced. In the processing space, a target serving as the raw material for the thin film and a substrate are placed facing each other. A permanent magnet and, if necessary, a holder or other device for holding the target are placed behind the target.

[0054] The magnetic field of the permanent magnet can constrain the spiral trajectory of electrons present in the processing space, generating a high-density plasma region. The presence of the high-density plasma region promotes ionization of the inert gas, and the ions collide with the target, generating target microparticles, which then adhere to the substrate, forming a thin film.

[0055] The RF output during RF magnetron sputtering is not particularly limited and may be adjusted to achieve an appropriate film formation rate. The temperature of the substrate during film formation is preferably controlled to be between room temperature and approximately 100°C.

[0056] The infrared absorption spectrum of the vapor-deposited layer (B) is 1575 m －１ Absorption peak height A at wavenumber of 1575 cm －１ The peak ratio (A1575 / A1687) of the absorption peak height A1687 at a wavenumber of 0.1 to 5.0 is 1575 cm －１ That is, the C═O stretching vibration usually attributed to carboxylate (—COO—) is the absorption peak height of 1600 cm －１ ~1500cm －１In the infrared light wavenumber region of 1575 cm －１ In addition, A1687 is an infrared absorption peak that is separate and independent from the A1575, and has an absorption maximum at 1687 cm －１ That is, the C═O stretching vibration usually attributed to a carboxy group (—COOH) has a peak height of 1800 cm －１ ~1600cm －１ In the infrared wavenumber region of 1687 cm －１ The film gives an absorption peak with an absorption maximum around 1575°C. The absorbance of the film is proportional to the amount of infrared-active chemical species present in the film. Therefore, the peak ratio (A1575 / A1787) of the infrared absorption spectrum can be used as a measure of the ratio of the amount of salts (-COO-) of carboxy groups that have formed salts with polyvalent metals to the amount of free carboxy groups (-COOH) in the film. The peak ratio A1575 / A1687 of the infrared absorption spectrum is preferably 0.1 to 5.0, more preferably 0.2 to 4.0, and particularly preferably 0.3 to 3.5.

[0057] The infrared absorption spectrum can be measured using, for example, an FT / IR-6800 manufactured by JASCO Corporation. Specifically, the infrared absorption spectrum of a sample film is measured by a transmission method, an ATR method (attenuated total reflection method), a KBr pellet method, a diffuse reflection method, a photoacoustic method (PAS method), or the like, and the peak heights (at the maximum absorption wavenumber) or peak areas of both absorption spectra are measured, and the ratio between the two can be determined. From the viewpoint of simplicity, the transmission method and the ATR method are preferred for measuring the infrared absorption spectrum. Typical examples of conditions for measuring the peak ratio of the infrared absorption spectrum in the ATR method include an incident angle of 65 degrees and a resolution of 4 cm. －１ , and measurements with 100 accumulations can be cited.

[0058] In the vapor-deposited layer (B), the area of ​​particles of 20 nm or larger is preferably 1% or less of the film area. Forming the vapor-deposited layer (B) with particles of 20 nm or smaller results in a dense vapor-deposited layer, achieving high oxygen barrier properties. Problems during vapor deposition, such as splashing, can occur, in which material is scattered. Splashing can generate coarse particles, but as long as the amount is 1% or less of the film area, it does not affect the oxygen barrier properties. The area of ​​particles of 20 nm or larger is preferably 1% or less of the film area, the area of ​​particles of 18 nm or larger is preferably 1% or less of the film area, and it is particularly preferred that the area of ​​particles of 15 nm or larger is 1% or less of the film area. Measurement of coarse particles can be performed, for example, using a scanning microscope JSM-6010PLUS / LA manufactured by JEOL Ltd. Specifically, secondary electron images can be measured at an accelerating voltage of 15 kV and a magnification of 20,000x.

[0059] (Coating Layer) The gas barrier film of the present invention may be formed by vapor-depositing the (B) layer on a plastic film, and then laminating a coating layer coated with a coating agent on the surface of the (B) layer or on the back surface of the plastic film. In addition, when the gas barrier film of the present invention has the (A) layer, the (A) layer may be vapor-deposited on a plastic film, and then vapor-depositing the (B) layer, and then laminating a coating layer coated with a coating agent on the surface of the (B) layer or on the back surface of the plastic film.

[0060] In the present invention, the coating method for these coating layers is not particularly limited, and any known and commonly used coating method can be used, such as roll coating, spraying, spin coating, blade coating, dipping, screen printing, inkjet printing, doctor roll coating, doctor blade coating, curtain coating, slit coating, dispensing, etc. Examples of the coating layer include a hard coating layer coated with a hard coating agent intended to protect the gas barrier film of the present invention, and coating layers having various functions, such as a heat-resistant coating layer coated with a coating agent having heat resistance as described below.

[0061] (Second Layer) The gas barrier film of the present invention can be bonded to another plastic film using an adhesive. Alternatively, another plastic layer can be formed on the gas barrier film by extrusion. (Hereinafter referred to as the second layer) The second layer may be made of the same type of resin material as the plastic film, or a different resin material. When the gas barrier film of the present invention is used as a packaging material, a polyolefin resin having heat sealing suitability can be selected, assuming that the second layer will be used as a sealant layer. Examples of the heat-sealable layer include polyethylene resins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), polypropylene (CPP), ethylene-propylene copolymers, and polymethylpentene; ethylene-vinyl acetate copolymers (EVA), ethylene-methyl methacrylate copolymers (EMMA), ethylene-ethyl acrylate copolymers (EEA), ethylene-methyl acrylate (EMA) copolymers, ethylene-ethyl acrylate-maleic anhydride copolymers (E-EA-MAH), ethylene-acrylic acid copolymers (EAA), and ethylene-methacrylic acid copolymers (EMAA); and ionomers of ethylene-acrylic acid copolymers and ionomers of ethylene-methacrylic acid copolymers, which may be used alone or in combination of two or more. When the second layer is a heat-sealable layer, its thickness can be adjusted appropriately depending on the purpose, but is, for example, 1 μm to 10 μm, and more preferably 3 μm to 10 μm, from the viewpoints of aroma retention and heat-sealability.

[0062] (Adhesive) The adhesive used to bond the second layer to the gas barrier film of the present invention may be any adhesive that can be used in a general-purpose lamination method. Examples of lamination methods include dry lamination, wet lamination, non-solvent lamination, and extrusion lamination. The adhesive becomes an adhesive layer after curing or drying.

[0063] The adhesive used in the dry lamination may be, for example, a one-component or two-component curable or non-curable vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, or other solvent-based, aqueous, or emulsion adhesive. A two-component curable adhesive may be a two-component curable adhesive composed of a polyol and an isocyanate compound. The laminating adhesive may be applied by, for example, direct gravure roll coating, gravure offset roll coating, kiss coating, reverse roll coating, Fountain coating, transfer roll coating, or other methods. For example, the DIC Dry series manufactured by DIC Corporation may be preferably used.

[0064] Various types of adhesives can also be used, and it is preferable to use a pressure-sensitive adhesive. Examples of pressure-sensitive adhesives include rubber-based adhesives obtained by dissolving polyisobutylene rubber, butyl rubber, or mixtures thereof in organic solvents such as benzene, toluene, xylene, and hexane, or these rubber-based adhesives blended with tackifiers such as abiethylene acid rosin ester, terpene-phenol copolymer, and terpene-indene copolymer, and acrylic-based adhesives obtained by dissolving an acrylic copolymer having a glass transition temperature of −20° C. or lower, such as a 2-ethylhexyl acrylate-n-butyl acrylate copolymer or a 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer, in an organic solvent.

[0065] The adhesive may be a functional adhesive. For example, an adhesive having gas barrier properties may be the oxygen barrier adhesive PASLIM series manufactured by DIC Corporation, which is a two-component reactive adhesive of polyester polyol and an isocyanate compound. The gas barrier adhesive becomes a gas barrier adhesive layer after curing or drying. Use of a gas barrier adhesive is preferred because it can further enhance the gas barrier properties of the laminate of the present invention.

[0066] When the adhesive is solvent-based, the adhesive is applied to one substrate using a roll such as a gravure roll, and the organic solvent is evaporated by heating in an oven or the like, and then the other substrate is laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 80°C, and the aging time is preferably 12 to 240 hours.

[0067] When the adhesive is solventless, the aroma-retaining adhesive, which has been preheated to about 40°C to 100°C, is applied to one substrate using a roll such as a gravure roll, and the other substrate is immediately laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 70°C, and the aging time is preferably 6 to 240 hours.

[0068] The amount of adhesive to be applied is adjusted as appropriate. In the case of a solvent-based adhesive, for example, the solid content is 1 g / m ２ 10g / m or more ２ Preferably 1 g / m or less ２ 5g / m or more ２ In the case of a solvent-free type, the amount of adhesive applied is adjusted to, for example, 1 g / m ２ 10g / m or more ２ Preferably 1 g / m or less ２ 5g / m or more ２ The following is the result.

[0069] (Heat-Resistant Resin Layer) The gas barrier film of the present invention may have a heat-resistant coating layer. The heat-resistant coating layer is a coating layer of a heat-resistant coating agent (hereinafter, sometimes simply referred to as a heat-resistant coating agent). Commercially available products can be used as the heat-resistant coating agent. Examples of commercially available products include SUNSYS FS241 manufactured by Sun Chemical Co., DH-S004 / DH-HARDENER P-60 manufactured by DIC Corporation, and ThermaGloss (registered trademark) 463 manufactured by Michelman.

[0070] Also preferred are heat-resistant coating agents containing compounds having a cellulose skeleton, a benzene ring skeleton, an isocyanuric ring skeleton, or an alicyclic skeleton, whose homopolymer glass transition temperature (hereinafter sometimes referred to as Tg) is 100°C or higher. Specific examples include cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose propionate, and cellulose butyrate; polyester resins having a benzene ring such as phthalic acid, naphthalenedicarboxylic acid, and an ethylene oxide (hereinafter sometimes referred to as EO) adduct of bisphenol A, and / or an alicyclic skeleton such as cyclopentanediol and dimethyloltricyclodecane; aromatic isocyanates such as diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, and naphthalene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and norbornene diisocyanate; and / or urethane resins obtained by combining isocyanuric triisocyanate with a polyol and / or tris(2-hydroxyethyl)isocyanurate. Polyisocyanates using the above-mentioned isocyanates may also be used as the curing agent. In addition, compounds having a benzene ring and an unsaturated double bond, such as styrene and phenoxydiethylene glycol acrylate, and / or compounds having an alicyclic structure and an unsaturated double bond, such as isobornyl acrylate and dicyclopentanyl acrylate, and radical copolymers such as (meth)acrylates are also preferably used. Furthermore, in consideration of adhesion to olefin films, a resin with a low Tg may be mixed in and used. The total amount of the cellulose skeleton, benzene ring skeleton, isocyanuric ring skeleton, and alicyclic skeleton of the aforementioned compounds is preferably 20 to 99% by mass, and more preferably 30 to 95% by mass, of the solid content of the heat-resistant coating layer (A).

[0071] The heat-resistant coating agent may be colored. The colorant is not particularly limited, and examples thereof include inorganic pigments, organic pigments, and dyes used in general inks, paints, and recording agents, such as those used in the printing layer (E) described below. Among these, pigments are preferred. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, and carbon black pigments. Other examples include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, cromophtal yellow, cromophtal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, etc. In addition, both non-acid-treated pigments and acid-treated pigments can be used.

[0072] Examples of inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithopone, antimony white, and gypsum. Among the inorganic pigments, titanium oxide is particularly preferred. Titanium oxide exhibits a white color and is preferred in terms of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, titanium oxide is preferably treated with silica and / or alumina. Examples of inorganic pigments other than white include aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, iron black, and zircon. Aluminum is in powder or paste form, but is preferably used in paste form from the viewpoints of handleability and safety. Whether leafing or non-leafing is used is appropriately selected from the viewpoints of brightness and density.

[0073] Furthermore, the heat-resistant coating agent preferably uses inorganic fine particles such as alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.) as aggregates due to their excellent heat resistance. Alternatively, boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc. are preferred due to their excellent thermal conductivity. The inorganic fine particles may be used alone or in combination. The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous silica may be used. For example, commercially available hollow silica fine particles such as Silinax manufactured by Nittetsu Mining Co., Ltd. may be used.

[0074] The primary particle diameter of the inorganic fine particles is preferably in the range of 5 nm to 100 μm. If the diameter is 1 nm or more, the inorganic fine particles are well dispersed in the dispersion, and if the diameter is 100 μm or less, the strength of the cured product is good. It is more preferably 10 nm to 20 μm. The inorganic fine particles can be blended in a ratio of 5 to 90 wt % based on the total solid content of the heat-resistant coating agent and the inorganic fine particles, and the blending amount can be changed as needed depending on the purpose. In particular, a ratio of 20 mass % or more is preferable.

[0075] Waxes, silicon additives, and organic beads can be added to the heat-resistant coating agent to prevent scratches on the coated film, prevent blocking during laminate formation, and improve processability during bag manufacturing after the laminate is produced. Specifically, waxes such as amide wax, polypropylene wax, polyethylene wax, paraffin wax, carnauba wax, and rice wax, ethylene oxide (EO) adducts of dimethylsiloxane, silicon additives of modified silicon, and organic beads made of acrylic, nylon, urethane, or epoxy can be added.

[0076] The solvent used in the heat-resistant coating agent is not particularly limited, and examples thereof include water, aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100, Solvesso #150, etc., aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, decane, etc., and various ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc. Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and glycol ethers such as ethylene glycol (mono- and di-)methyl ether, ethylene glycol (mono- and di-)ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono- and di-)methyl ether, diethylene glycol (mono- and di-)ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono- and di-)methyl ether, propylene glycol (mono- and di-)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono- and di-)methyl ether. These can be used alone or in combination of two or more. Furthermore, to more effectively carry out coating, an antifoaming agent or a leveling agent can be used.

[0077] The amount of the heat-resistant resin layer to be applied is appropriately selected depending on the application, but the amount of the applied heat-resistant resin layer after drying is preferably 0.01 to 100 g / m ２ is preferably 0.1 to 50 g / m ２ More preferably, 0.5 to 3 g / m ２ is particularly preferred.

[0078] (Laminate Structure) An example of a specific embodiment of the gas barrier film of the present invention is given below. Of course, the laminate of the present invention is not limited to this embodiment. Plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / second layer Plastic film / printed layer / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / second layer Printed layer / plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / second layer Plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / printed layer / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / printed layer / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Printed layer / plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0079] Plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Plastic film / printed layer / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / printed layer / gas barrier adhesive layer / second layer Printed layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / printed layer / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / printed layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Printed layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0080] Heat-resistant resin layer / plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / deposited layer (A) / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0081] Heat-resistant resin layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / printed layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / vapor-deposited layer (A) / vapor-deposited layer (B) / vapor-deposited protective coating layer / printed layer / gas-barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / vapor-deposited layer (A) / vapor-deposited layer (B) / vapor-deposited protective coating layer / gas-barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0082] Heat-resistant resin layer / plastic film / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / gas barrier adhesive layer / second layer A coating layer that imparts functions such as release properties and antistatic properties may also be present on the plastic film.

[0083] Plastic film / deposited layer (B) / gas barrier adhesive layer / second layer Plastic film / printed layer / deposited layer (B) / gas barrier adhesive layer / second layer Printed layer / plastic film / deposited layer (B) / gas barrier adhesive layer / second layer Plastic film / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / printed layer / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Printed layer / plastic film / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0084] Plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Plastic film / printed layer / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / printed layer / gas barrier adhesive layer / second layer Printed layer / plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / printed layer / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / printed layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Printing layer / plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0085] Heat-resistant resin layer / plastic film / deposited layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / deposited layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / deposited layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0086] Heat-resistant resin layer / plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / printed layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor deposition layer (B) / vapor deposition protective coating layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / vapor-deposited layer (B) / vapor-deposited protective coating layer / printed layer / gas-barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / vapor-deposited layer (B) / vapor-deposited protective coating layer / gas-barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer

[0087] (Packaging Material) The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting food, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, usage environment, and usage form. In addition, the packaging of the present invention may be appropriately provided with an easy-open treatment or resealable means.

[0088] Taking a laminate having a sealant layer as an example of the packaging material of the present invention, the laminates are stacked with the sealant layer surfaces facing each other, and then the peripheral edges are heat-sealed to form a bag. Examples of bag-making methods include folding or stacking the laminate of the present invention so that the inner layer surfaces (sealant layer surfaces) face each other, and heat-sealing the peripheral edges using, for example, a side seal, two-sided seal, three-sided seal, four-sided seal, envelope seal, flared seal, flat-bottom seal, square-bottom seal, gusset seal, or other heat seal methods. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage pattern. Self-standing packaging materials (standing pouches) are also possible. Heat sealing can be performed using known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0089] When the plastic film and second substrate of the laminate of the present invention do not function as a sealant layer that serves as a heat-sealed portion when forming a packaging material, a further sealant layer may be added. The sealant layer may be an additional substrate bonded with the adhesive of the present invention, or may be an adhesive layer made of the adhesive of the present invention.

[0090] The packaging material of the present invention is filled with contents through its opening, and then the opening is heat-sealed to produce a product using the packaging material of the present invention. Examples of contents to be filled include foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snacks; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, rice porridge, packaged rice cakes, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; processed livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and processed fish ham and meat products. Examples of such foods include processed seafood products such as sausages, fish paste products, kamaboko, nori seaweed, tsukudani (simmered foods in soy sauce), bonito flakes, salted fish, smoked salmon, and spicy mentaiko; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as frozen and chilled prepared dishes, including hamburgers, meatballs, fried seafood, gyoza, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0091] In addition, the present invention can also be used as a packaging material for various non-food products, such as cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and emulsion, vacuum insulation materials, batteries, etc.

[0092] In particular, the packaging material of the present invention has excellent hydrogen sulfide adsorption capacity, and therefore exhibits its performance when the contents contain sulfur. For example, since it has the effect of reducing the retort odor generated during retort, it is suitable as a packaging material for retort pouch foods. Furthermore, since it can adsorb hydrogen sulfide generated by the penetration of moisture, it is also suitable as an exterior material for all-solid-state lithium-ion batteries.

[0093] (Recycled Plastics) The laminate or packaging material of the present invention can also be processed directly using various known recycling plastic processing methods to produce recycled plastics. As an example of a specific embodiment, recycled plastics can be obtained by a production method including a step of crushing the recovered material obtained by separating the laminate of the present invention into each substrate, or the laminate or packaging material of the present invention, a step of melt-kneading the crushed film pieces, and a step of pelletizing the melt-kneaded mixture.

[0094] The crusher used for crushing (pulverization) may be any known crusher and is not particularly limited. The crushed film pieces are then physically blended using melt kneading, solvent cast blending, latex blending, polymer complexing, or the like. The melt kneading method is particularly common. Examples of kneading devices include a tumbler, Henschel mixer, rotary mixer, super mixer, ribbon tumbler, and V-blender. The film is melt-kneaded using such a kneading device and then pelletized. A single-screw or multi-screw extruder is typically used for melt kneading and pelletization. The film pieces may be fed as they are or may be subjected to a compression volume reduction treatment with or without heating before being fed. In addition to these extruders, a Banbury mixer, roller, Ko-kneader, blast mill, Prabender Bloutograph, or the like may also be used, and these may be operated batchwise or continuously. Alternatively, the film may be used as a molding resin without being melt-kneaded, and melt-kneaded in the heating barrel of a molding machine.

[0095] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0096] (Examples 1 to 3) A magnetron sputtering device (Model EB1100, manufactured by Canon Anelva Corporation) was used as the sputtering device. A mixture of zinc and terephthalic acid (molar ratio, zinc:terephthalic acid = 4:1) was used as the target, and a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide was used as the substrate film. Argon was used as the process gas to form a vapor-deposited layer (B). The sputtering power supply power was 5.0 W / cm ２ The deposition pressure was 0.4 Pa. The gas barrier films of Examples 1 to 3 were obtained by controlling the deposition time.

[0097] (Example 4) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a mixture of zinc and terephthalic acid (molar ratio of zinc:terephthalic acid = 8:1) as a target, thereby obtaining a gas barrier film of Example 4.

[0098] (Example 5) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a mixture of magnesium and terephthalic acid (molar ratio, magnesium:terephthalic acid = 1:1) as a target, thereby obtaining a gas barrier film of Example 5.

[0099] (Example 6) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a mixture of calcium and terephthalic acid (molar ratio, calcium:terephthalic acid = 2:1) as a target, thereby obtaining a gas barrier film of Example 6.

[0100] (Example 7) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of zinc and terephthalic acid (molar ratio, zinc:terephthalic acid = 4:1) as the target, thereby obtaining a gas barrier film of Example 7.

[0101] (Example 8) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of zinc and terephthalic acid (molar ratio, zinc:terephthalic acid = 8:1) as the target, thereby obtaining a gas barrier film of Example 8.

[0102] (Example 9) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of magnesium and terephthalic acid (molar ratio, magnesium:terephthalic acid = 1:1) as the target, thereby obtaining a gas barrier film of Example 9.

[0103] (Example 10) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of calcium and terephthalic acid (molar ratio, calcium:terephthalic acid = 2:1) as the target, thereby obtaining a gas barrier film of Example 10.

[0104] (Example 11) Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide was used as the substrate film, and a mixture of zinc and pyromellitic acid (molar ratio of zinc:pyromellitic acid = 2:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 11.

[0105] (Example 12) Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide was used as the substrate film, and a mixture of zinc and pyromellitic acid (molar ratio of zinc:pyromellitic acid = 3:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 12.

[0106] (Example 13) Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide was used as the substrate film, and a mixture of zinc and pyromellitic acid (molar ratio of zinc:pyromellitic acid = 5:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 13.

[0107] (Example 14) Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the base film, and a mixture of zinc and pyromellitic acid (molar ratio of zinc:pyromellitic acid = 2:1) was used as the target to form a vapor deposition layer (B), thereby obtaining a gas barrier film of Example 14.

[0108] (Example 15) Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the base film, and a mixture of zinc and pyromellitic acid (molar ratio, zinc:pyromellitic acid=3:1) was used as the target to form a vapor deposition layer (B), thereby obtaining a gas barrier film of Example 15.

[0109] (Example 16) Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the base film, and a mixture of zinc and pyromellitic acid (molar ratio, zinc:pyromellitic acid=5:1) was used as the target to form a vapor deposition layer (B), thereby obtaining a gas barrier film of Example 16.

[0110] Example 17 Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and a mixture of zinc and acrylic acid (molar ratio of zinc:acrylic acid = 6:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 17.

[0111] (Example 18) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of zinc and acrylic acid (molar ratio, zinc:acrylic acid = 6:1) as the target, thereby obtaining a gas barrier film of Example 18.

[0112] Example 19 Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide was used as the substrate film, and a mixture of zinc and citric acid (molar ratio of zinc:citric acid = 2:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 19.

[0113] (Example 20) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of zinc and citric acid (molar ratio, zinc:citric acid = 2:1) as the target, thereby obtaining a gas barrier film of Example 20.

[0114] Example 21 Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and a mixture of zinc and phthalic acid (molar ratio of zinc:phthalic acid = 4:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 21.

[0115] (Example 22) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of zinc and phthalic acid (molar ratio of zinc:phthalic acid = 4:1) as the target, thereby obtaining a gas barrier film of Example 22.

[0116] (Example 23) Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and a mixture of zinc and isophthalic acid (molar ratio of zinc:isophthalic acid = 4:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 23.

[0117] (Example 24) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the base film and a mixture of zinc and isophthalic acid (molar ratio, zinc:isophthalic acid=4:1) as the target, thereby obtaining a gas barrier film of Example 24.

[0118] Example 25 Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide was used as the substrate film, and a mixture of zinc and trimellitic acid (molar ratio of zinc:trimellitic acid = 3:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining a gas barrier film of Example 25.

[0119] (Example 26) Under the same conditions as in Examples 1 to 3, a vapor deposition layer (B) was formed using a PET film (E5102, manufactured by Toyobo Co., Ltd.) as the substrate film and a mixture of zinc and trimellitic acid (molar ratio of zinc:trimellitic acid=3:1) as the target, thereby obtaining a gas barrier film of Example 26.

[0120] Example 27 Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and a mixture of zinc and 4,4'-dibenzoic acid (molar ratio, zinc:4,4'-dibenzoic acid = 3:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining the gas barrier film of Example 27.

[0121] (Example 28) Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the base film, and a mixture of zinc and 4,4'-dibenzoic acid (molar ratio, zinc:4,4'-dibenzoic acid = 3:1) was used as the target to form a vapor deposition layer (B), thereby obtaining a gas barrier film of Example 28.

[0122] Comparative Example 1 A transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having a vapor-deposited layer (A) of aluminum oxide without a vapor-deposited layer (B) was used.

[0123] (Comparative Example 2) Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and terephthalic acid was used as the target to form a terephthalic acid vapor-deposited layer, thereby obtaining the film of Comparative Example 2.

[0124] (Comparative Example 3) Under the same conditions as in Examples 1 to 3, a transparent vapor-deposited PET film (Barrierox 1011HG, manufactured by Toray Advanced Film Co., Ltd.) having an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and zinc was used as the target to form a zinc vapor-deposited layer, thereby obtaining the film of Comparative Example 3.

[0125] (Preparation of evaluation films) The evaluation films used were Film 1, which was the film of the Example or Comparative Example used as is; Laminated Film 2, which was the film of the Example or Comparative Example bonded to a non-oriented polypropylene film (hereinafter abbreviated as CPP film) using an adhesive; and Laminated Film 3, which was the laminated film 2 subjected to a bending test.

[0126] (Method for producing laminate film 2) The films of the Examples and Comparative Examples were prepared by blending DiCdry LX-830 and KW-75 (both manufactured by DIC Corporation) in a blending ratio of 10 / 1.5, and adding ethyl acetate so that the nonvolatile content was 25%. The reactive adhesive was then applied onto the vapor-deposited layer (B) to a dry film thickness of 2.5 μm. The dilution solvent was evaporated using a dryer set at a temperature of 50° C., and the film was then laminated with a CPP film (P1128, manufactured by Toyobo Co., Ltd.). Aging was carried out at 40° C. for 3 days, and laminate film 2 was obtained.

[0127] (Method for producing laminate film 3) The laminate film 2 was adjusted to a size of 30 cm x 20 cm, and a bending test was carried out in accordance with ASTM F392 using a Gelbo Flex Tester (manufactured by Tester Sangyo Co., Ltd.) under the conditions of 440° / 90 mm linear motion 65 mm, 23°C, and 30 bending cycles, to obtain a laminate film 3.

[0128] (Evaluation Method) (Infrared Absorption Spectral Intensity Ratio (A1575 / A1687)) The infrared absorption spectral intensity ratio (A1575 / A1687) was measured for Film 1. Using FT / IR-6800 manufactured by JASCO Corporation, the ATR method was performed at an incident angle of 65 degrees and a resolution of 4 cm. －１ The infrared absorption spectrum of the film was measured under the conditions of 100 times of accumulation, and 1575 cm －１ and 1687 cm －１ The peak ratio A1575 / A1687 was calculated from the ratio of the peak heights of the two peaks.

[0129] (Presence or Absence of Coarse Particles) The presence or absence of coarse particles was measured for Film 1. Using a scanning microscope JSM-6010PLUS / LA manufactured by JEOL Ltd., secondary electron images were observed at an acceleration voltage of 15 kV and a magnification of 20,000 times to confirm the presence or absence of coarse particles of 20 nm or more.

[0130] (Evaluation of gas barrier properties: oxygen permeability) Oxygen permeability (OTR) was measured for Film 1, Laminate Film 2, and Laminate Film 3. The measurement was carried out in accordance with JIS-K7126 (constant pressure method) using an oxygen permeability measuring device OX-TRAN2 / 22 manufactured by Mocon Co., Ltd., under an atmosphere of a temperature of 23°C and a humidity of 90% RH. RH represents relative humidity. The unit of oxygen permeability is cc / day·atm·m2.

[0131] (Evaluation of hydrogen sulfide adsorption capacity) The hydrogen sulfide adsorption capacity was evaluated for laminate film 2. The film was cut to a size of 5 cm x 5 cm, placed in a smell bag, and heat-sealed. 3 L of air was sealed inside, and hydrogen sulfide gas was added to a concentration of 20 ppm. This was left to stand, and after a certain period of time (10 minutes, 1 hour, 3 hours, 6 hours, and 24 hours), the gas concentration inside the bag was measured using a gas detector tube. An undeposited film was used as a control, and films that showed a decrease in hydrogen sulfide gas concentration were judged to have hydrogen sulfide adsorption capacity.

[0132] The film configurations and evaluation results of the examples are shown in Tables 1 to 4, and the film configurations and evaluation results of the comparative examples are shown in Table 5.

[0133]

[0134]

[0135]

[0136]

[0137]

[0138] Examples 1 to 28 had good oxygen barrier properties under high humidity and / or after the flex test. On the other hand, Comparative Examples 1 to 3 had poorer oxygen barrier properties under high humidity and / or after the flex test than the Examples. Furthermore, the Examples and Comparative Examples using zinc as the metal compound had hydrogen sulfide adsorption ability.

Claims

1. A gas barrier film characterized by having, on a plastic film, a vapor-deposited layer (B) containing at least one metal element selected from the group consisting of zinc, magnesium, and calcium, and a compound having a carbonyl group.

2. 1575 m in the infrared absorption spectrum of the vapor-deposited layer (B) －１ Absorption peak height A at wavenumber of 1575 cm －１ 2. The gas barrier film according to claim 1, wherein the peak ratio (A1575 / A1687) of absorption peak heights A1687 at wavenumbers of 0.1 to 5.

0.

3. The gas barrier film according to claim 1, wherein the thickness of the vapor-deposited layer (B) is in the range of 1 to 200 nm.

4. The gas barrier film according to claim 1, wherein the area of ​​particles of 20 nm or larger in the vapor deposition layer (B) is 1% or less of the film area.

5. A gas barrier film according to claim 1, which comprises a vapor-deposited layer (A) of aluminum oxide and / or silicon oxide and the layer (B) in this order on a plastic film.

6. The gas barrier film according to claim 1, wherein the layer (B) is a vapor-deposited layer (B) of a mixture of at least one metal selected from the group consisting of zinc, magnesium, and calcium and at least one carboxylic acid-containing compound selected from terephthalic acid, pyromellitic acid, acrylic acid, citric acid, phthalic acid, isophthalic acid, trimellitic acid, and 4,4'-dibenzoic acid.

7. A package containing the gas barrier film according to any one of claims 1 to 6.

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