Gas barrier film and packaging

Abstract

A gas barrier film having 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, and a package containing the gas barrier film. -1 Absorption peak height A at wavenumbers of 1575 to 1687 cm -1 It is preferable that the peak ratio (A1575 / A1687) of the absorption peak height A1687 at this wave number is 0.1 to 5.0.

Description

[Technical Field]

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

[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 and flavor from changing and their efficacy from decreasing due to oxidation. Resin films with vapor deposition layers are used because they can provide high barrier properties at low cost. Known examples of gas barrier films having a vapor-deposited film 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. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-253319 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-069389 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[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. [Effects of the Invention]

[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. DETAILED DESCRIPTION OF THE INVENTION

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

[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 used as the substrate in the present invention is not particularly limited, and it can be a plastic film used as a packaging material for packaging food, medicine, etc. Specific examples include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, nylon film, polyacrylonitrile film, polyolefin films such as polyethylene film (OPE: biaxially oriented polyethylene film, LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film) and polypropylene film (CPP: non-oriented polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, cellophane, etc.

[0012] When considering mono-material packaging, a film made of a thermoplastic resin whose main component is an olefin-based resin can be used as the substrate. Specific examples of olefin-based 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-based 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 made from biomass materials are also available, classified by their biomass plastic content as specified by ISO 16620 or ASTM D6866. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 1012 particles, and this rate remains 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, or biomass plastic content, can be determined. Examples of plant-derived low-density polyethylene that 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, as an alternative to conventional polyolefin films made from petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films containing polyethylene resins made from biomass-derived ethylene glycol are also known. The polyethylene resin is not particularly limited except that ethylene glycol derived from biomass is used as part of the raw material, and examples thereof include ethylene homopolymers and copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units), and 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 thereof 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 resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. Among them, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of making it even more difficult for damage such as holes or tears to occur even when films rub against each other, and has 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), which will be described later. 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 extrusion, cast molding, T-die, cutting, inflation, etc. The film may be an unstretched film, or may be stretched uniaxially or biaxially using a tenter system, a tubular system, 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 from the viewpoint 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] (Printing layer) The printing layer is a layer on which letters, figures, symbols, and other desired designs are printed. There are no particular limitations on the printing method or printing ink, and any known printing method or printing ink 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 films 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 water-based 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 at which 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 film.

[0026] The resin used in the liquid ink is not particularly limited, and examples thereof include 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 can be used in combination. Preferably, at least one 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 solvents used preferably do not contain aromatic hydrocarbon organic solvents. More specifically, 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.

[0029] (Vapor-deposited layer (A) of aluminum oxide and / or silicon oxide) The plastic film may have a vapor-deposited layer (A) of aluminum oxide (also called aluminum oxide, alumina, or AlOx, which is various aluminum oxides such as AlO and Al2O3, or a mixture thereof) and / or silicon oxide (also called silicon oxide, silica, or SiOx, which is various silicon oxides such as SiO and SiO2, or a mixture thereof). When the vapor-deposited layer (A) is present, the vapor-deposited layer (A) is provided between the plastic film and the vapor-deposited layer (B) described below.

[0030] The vapor deposition layer (A) is preferably formed by a vapor phase thin film formation method. Vapor phase thin film formation methods used to form the vapor deposition 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 are obtained. As described above, the vapor phase thin film formation method used in the present invention is not particularly limited, but production by a PVD method such as vacuum deposition, sputtering, or ion plating is preferred because it allows for the easy formation of a stable thin film, and further, thin film formation by vacuum deposition is most preferred.

[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 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, or vacuum swing conditions, or in air or an inert gas atmosphere. By carrying out the process under reduced pressure or vacuum, it is possible to increase the evaporation rate and lower the evaporation temperature, while pressurization can promote precipitation of the evaporated material. Furthermore, by using a vacuum or inert atmosphere, oxidation of the metal, metal oxide, metal hydroxide, etc., and the support can be controlled. Furthermore, if oxidation during the vapor deposition process can be controlled and 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 below Pa and into which an inert gas (e.g., argon) has been introduced. In the processing space, a target, which is 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 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, which may result in problems such as variations in gas barrier properties within the substrate surface. If the layer thickness is thicker than 500 nm, the residual stress within the vapor-deposited layer (A) may increase, which may cause cracks in the vapor-deposited layer (A) under high-temperature and high-humidity environments, resulting in problems with 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. A composite oxide of aluminum oxide and silicon oxide is particularly preferred. In other words, 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, as well as 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 mentioned 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 molar ratio of the metal element to the compound having a carbonyl group in the vapor-deposited layer (B) is 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. 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 more preferably a mixture of a metal and a carbonyl group-containing compound. By using the mixture to simultaneously vapor-deposit the metal compound and the carbonyl group-containing compound, a vapor-deposited layer (B) in which the carbonyl group-containing compound is ionically crosslinked can be obtained. 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: a metal compound target such as a metal, metal oxide, or metal hydroxide, and a carbonyl group-containing compound target. Separating the targets for the metal compound and the carbonyl group-containing compound makes it possible to control the deposition amount of each. By simultaneously depositing the metal compound and the carbonyl group-containing compound, a deposition layer in which the carbonyl group-containing compound is ionically crosslinked can be obtained in the deposition layer (B). The deposition amount of each compound 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, calculated as the molar ratio of the metal compound to the carbonyl group-containing compound.

[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 ionic crosslinking concentration 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, or vacuum swing conditions, or in air or an inert gas atmosphere. By carrying out the process under reduced pressure or vacuum, it is possible to increase the evaporation rate and lower the evaporation temperature, while pressurization can promote precipitation of the evaporated material. Furthermore, by using a vacuum or inert atmosphere, oxidation of the metal, metal oxide, metal hydroxide, etc., and the support can be controlled. Furthermore, if oxidation during the vapor deposition process can be controlled and 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 product 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 below Pa and into which an inert gas (e.g., argon) has been introduced. In the processing space, a target, which is 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 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 wavenumbers of 1575 to 1687 cm -1 The peak ratio (A1575 / A1687) of the absorption peak height A1687 at the wavenumber of 0.1 to 5.0. A1575 is the 1575cm peak attributed to the salt of the carboxyl group. -1This is the absorption peak height of the infrared absorption spectrum of the C=O stretching vibration of carboxylic acid salts (-COO-). -1 ~1500cm -1 In the infrared wavenumber region of 1575 cm -1 It gives an absorption peak with an absorption maximum around it. In addition, A1687 is an infrared absorption peak that is separate and independent from the A1575, and is the 1687 cm -1 This is the peak height of the C=O stretching vibration in the infrared absorption spectrum. That is, the C=O stretching vibration usually attributed to the carboxyl group (-COOH) is 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. The absorbance of the film is proportional to the amount of infrared-active chemical species present in the film. Therefore, the peak ratio of the infrared absorption spectrum (A1575 / A1787) can be used as a measure of the amount of salts (-COO-) of carboxyl groups that have formed salts with polyvalent metals and free carboxyl groups (-COOH) in the film. The peak ratio A1575 / A1687 in the infrared absorption spectrum is preferably from 0.1 to 5.0, more preferably from 0.2 to 4.0, and particularly preferably from 0.3 to 3.5.

[0057] The infrared absorption spectrum can be measured using, for example, 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 more is preferably 1% or less of the film area. By forming the vapor-deposited layer (B) with particles of 20 nm or less, a dense vapor-deposited layer can be obtained, and high oxygen barrier properties can be achieved. Problems during vapor deposition can cause a phenomenon known as splash, in which material scatters. Splash can produce large particles, but as long as they account for 1% or less of the film's area, they will not affect the oxygen barrier properties. It is preferable that the area of ​​particles of 20 nm or larger is 1% or less of the film area, it is preferable that the area of ​​particles of 18 nm or larger is 1% or less of the film area, and it is particularly preferable that the area of ​​particles of 15 nm or larger is 1% or less of the film area. The measurement of coarse particles can be carried out using, for example, 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 an observation magnification of 20,000 times.

[0059] (coating layer) The gas barrier film of the present invention may be formed by 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. Alternatively, when the gas barrier film has the (A) layer, the (A) layer may be deposited on a plastic film, and then the (B) layer may be deposited, and then a coating layer coated with a coating agent may be laminated on the surface of the (B) layer or on the back surface of the plastic film.

[0060] In the present invention, the method for applying 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, ink jet printing, doctor roll coating, doctor blade coating, curtain coating, slit coating, or dispensing. Examples of the coating layer include a hard coat coating layer coated with a hard coat agent intended to protect the gas barrier film of the present invention, and a coating layer 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 (hereinafter referred to as the second layer) can be formed on the gas barrier film by extrusion. The second layer may be made of the same 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-sealability can be selected, assuming that the second layer will be used as a sealant layer. Examples of suitable resins 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. These may be used alone or in combination. When the second layer is a heat seal layer, its thickness can be adjusted appropriately depending on the purpose, but from the viewpoint of aroma retention and heat sealability, it is, for example, 1 μm to 10 μm, more preferably 3 μm to 10 μm.

[0062] (glue) 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, such as 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 adhesive, cured or non-cured, such as a vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, or other solvent-based, water-based, or emulsion-based adhesive. A two-component curing adhesive may be a two-component curing adhesive composed of a polyol and an isocyanate compound. The laminating adhesive may be coated 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, with pressure-sensitive adhesives being preferred. Examples of pressure-sensitive adhesives include rubber-based adhesives prepared by dissolving polyisobutylene rubber, butyl rubber, or mixtures thereof in organic solvents such as benzene, toluene, xylene, or hexane, or those prepared by blending these rubber-based adhesives with tackifiers such as abiethoxylated rosin esters, terpene-phenol copolymers, or terpene-indene copolymers, or acrylic-based adhesives prepared by dissolving acrylic copolymers with a glass transition temperature of −20° C. or lower, such as 2-ethylhexyl acrylate-n-butyl acrylate copolymers or 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymers, in organic solvents.

[0065] The adhesive may be a functional adhesive. For example, an adhesive having gas barrier properties may be the PASLIM series of oxygen barrier adhesives manufactured by DIC Corporation, which are two-component reactive adhesives of polyester polyol and isocyanate compound. The gas barrier adhesive becomes a gas barrier adhesive layer after curing or drying. The 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 attached 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. For example, in the case of a solvent-based adhesive, the solid content is 1 g / m 2 More than 10g / m 2 Less than 1 g / m 2 More than 5g / m 2 Adjust the amount of adhesive to be as follows: For solvent-free adhesive, the amount of adhesive to be applied is, for example, 1 g / m 2 More than 10g / m 2 Less than 1 g / m 2 More than 5g / m 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 coating agent having heat resistance (hereinafter, sometimes simply referred to as a heat-resistant coating agent). Commercially available heat-resistant coating agents can be used, such as 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 ethylene oxide (hereinafter sometimes referred to as EO) adducts 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 curing agents. Also preferably used are 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 of (meth)acrylate, etc. Also, in consideration of adhesion to olefin films, a resin with a low Tg may be mixed and used. The total amount of the cellulose skeleton, benzene ring skeleton, isocyanuric ring skeleton, and alicyclic skeleton of the above-mentioned compound 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 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 that has been treated with silica and / or alumina is preferred. 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 it is preferably used in paste form from the standpoints of handleability and safety, and whether leafing or non-leafing aluminum is used is selected appropriately from the standpoints of brightness and concentration.

[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, and ultrafine amorphous silica) as aggregates because they have excellent heat resistance. Alternatively, boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, and silicon oxide are preferred because they have 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 irregularly shaped particles can be used. For example, commercially available hollow silica fine particles such as Silinax manufactured by Nittetsu Mining Co., Ltd. can be used.

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

[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 created. 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-based 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. Antifoaming agents and leveling agents may also be used to more effectively coat the film.

[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 preferable, and 0.1 to 50 g / m 2 More preferably, 0.5 to 3 g / m 2 is particularly preferred.

[0078] (Laminated structure) An example of a specific embodiment of the gas barrier film of the present invention is given below, but the laminate of the present invention is not limited to this embodiment. Plastic film / vapor deposition layer (A) / vapor deposition layer (B) / gas barrier adhesive layer / second layer Plastic film / Printed layer / Vapor deposition layer (A) / Vapor deposition layer (B) / Gas barrier adhesive layer / Second layer Printing layer / Plastic film / Vapor deposition layer (A) / Vapor deposition layer (B) / Gas barrier adhesive layer / Second layer Plastic film / vapor deposition layer (A) / vapor deposition layer (B) / 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) / Gas barrier adhesive layer / Substrate used as intermediate layer / Adhesive layer / Second layer Printing layer / Plastic film / Vapor deposition layer (A) / Vapor deposition 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 / Printing 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 / printing layer / gas barrier adhesive layer / second layer Printing 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 / Printing 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 / printing layer / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Printing 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 / vapor deposition layer (A) / vapor deposition layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor deposition layer (A) / vapor deposition layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / Printed layer / Plastic film / Vapor deposition layer (A) / Vapor deposition layer (B) / Gas barrier adhesive layer / Second layer Heat-resistant resin layer / plastic film / vapor deposition layer (A) / vapor deposition layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor-deposited layer (A) / vapor-deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / vapor deposition layer (A) / vapor deposition 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 / printing 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 / printing layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / Printing 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 / printing 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 deposition layer (A) / vapor deposition layer (B) / vapor deposition protective coating layer / printing layer / gas barrier adhesive layer / substrate used as intermediate layer / 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 / 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 / printing layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / printing layer / plastic film / gas barrier adhesive layer / second layer Furthermore, the plastic film may have a coating layer on it that provides functions such as release properties and antistatic properties.

[0083] Plastic film / vapor deposition layer (B) / gas barrier adhesive layer / second layer Plastic film / Printed layer / Vapor deposition layer (B) / Gas barrier adhesive layer / Second layer Printing layer / plastic film / vapor deposition layer (B) / gas barrier adhesive layer / second layer Plastic film / vapor deposition layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Plastic film / Printed layer / Vapor deposition layer (B) / Gas barrier adhesive layer / Substrate used as intermediate layer / Adhesive layer / Second layer Printing layer / Plastic film / Vapor deposition 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 / printing layer / gas barrier adhesive layer / second layer Printing 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 / Printing 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 / printing 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 / vapor deposition layer (B) / gas barrier adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor deposition 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 / vapor deposition layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / plastic film / printed layer / vapor-deposited layer (B) / gas barrier adhesive layer / substrate used as intermediate layer / adhesive layer / second layer Heat-resistant resin layer / printed layer / plastic film / vapor deposition 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 / printing 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 / printing layer / gas barrier adhesive layer / second layer Heat-resistant resin layer / Printing 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 deposition layer (B) / vapor deposition protective coating layer / printing layer / gas barrier adhesive layer / substrate used as intermediate layer / 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 / 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 protecting foods, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the package of the present invention may be appropriately provided with an easy-open treatment or a resealable means.

[0088] Taking a laminate having a sealant layer as an example of the packaging material of the present invention, the laminate is 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 the laminate of the present invention or stacking it 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 the opening is then heat-sealed to produce a product using the packaging material of the present invention. Examples of contents that can be filled include foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snacks; bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, rice porridge, packaged rice cakes, and cereal foods; pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and fish, ham, and 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 plastic) 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 the steps 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, melting and kneading the crushed film pieces, and pelletizing the melt-kneaded mixture.

[0094] The crusher used for crushing (pulverizing) is not particularly limited and any known crusher may be used. The crushed film pieces are physically blended using methods such as melt mixing, solvent cast blending, latex blending, and polymer complexing. Melt mixing is particularly common. Examples of mixing devices include tumblers, Henschel mixers, rotary mixers, super mixers, ribbon tumblers, and V-blenders. The film pieces are melt-mixed using these mixers and then pelletized. Single- or multi-screw extruders are typically used for melt mixing and pelletization. The film pieces may be fed directly into the extruder or may be compressed with or without heating before being added. In addition to these extruders, Banbury mixers, roller mixers, Ko-kneaders, blast mills, and Prabender Bloutographs can also be used, operated batchwise or continuously. Alternatively, the film pieces may be used as molding resins without melt mixing and then melt-kneaded in the heating barrel of a molding machine. [Example]

[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.) with a vapor-deposited layer of aluminum oxide (A) was used as the substrate film. Argon was used as the process gas to form the deposition layer (B). The sputtering power was 5.0 W / cm. 2 The deposition pressure was 0.4 Pa. By controlling the deposition time, the gas barrier films of Examples 1 to 3 were obtained.

[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, 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 PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of zinc and terephthalic acid (molar ratio, zinc:terephthalic acid = 4:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the gas barrier film of Example 7.

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

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

[0103] Example 10 Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of calcium and terephthalic acid (molar ratio, calcium:terephthalic acid = 2:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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 an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and a mixture of zinc and pyromellitic acid (molar ratio, zinc:pyromellitic acid = 2:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining the 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 an aluminum oxide vapor-deposited layer (A) 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 the 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 an aluminum oxide vapor-deposited layer (A) 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 the 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 substrate film, and a mixture of zinc and pyromellitic acid (molar ratio, zinc:pyromellitic acid = 2:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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 substrate 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 the 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 substrate 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 the 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, zinc:acrylic acid = 6:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining the gas barrier film of Example 17.

[0111] Example 18 Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of zinc and acrylic acid (molar ratio, zinc:acrylic acid = 6:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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 an aluminum oxide vapor-deposited layer (A) was used as the substrate film, and a mixture of zinc and citric acid (molar ratio, zinc:citric acid = 2:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining the gas barrier film of Example 19.

[0113] Example 20 Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of zinc and citric acid (molar ratio, zinc:citric acid = 2:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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, zinc:phthalic acid = 4:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining the gas barrier film of Example 21.

[0115] Example 22 Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of zinc and phthalic acid (molar ratio, zinc:phthalic acid = 4:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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, zinc:isophthalic acid = 4:1) was used as the target to form a vapor-deposited layer (B), thereby obtaining the gas barrier film of Example 23.

[0117] Example 24 Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of zinc and isophthalic acid (molar ratio, zinc:isophthalic acid = 4:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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 an aluminum oxide vapor-deposited layer (A) 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 the gas barrier film of Example 25.

[0119] Example 26 Under the same conditions as in Examples 1 to 3, a PET film (E5102, manufactured by Toyobo Co., Ltd.) was used as the substrate film, and a mixture of zinc and trimellitic acid (molar ratio, zinc:trimellitic acid = 3:1) was used as the target to form a vapor deposition layer (B), thereby obtaining the 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 the 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] (Creating evaluation film) The films used for evaluation were Film 1, which was made by using the films of the Examples and Comparative Examples as they were; Laminated Film 2, which was made by bonding the films of the Examples and Comparative Examples with unstretched polypropylene film (hereinafter referred to as CPP film) using an adhesive; and Laminated Film 3, which was made by performing a bending test on Laminated Film 2.

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

[0127] (Method for manufacturing laminate film 3) 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 laminate film 3.

[0128] (Evaluation method) (Infrared absorption spectrum intensity ratio (A1575 / A1687)) The infrared absorption spectrum intensity ratio (A1575 / A1687) was measured for film 1. Using a JASCO FT / IR-6800, the ATR method was used, with an incident angle of 65 degrees and a resolution of 4 cm. -1 The infrared absorption spectrum of the film was measured under the condition of 100 times of accumulation, and the peak wavelength was 1575 cm -1 and 1687cm -1 The peak ratio A1575 / A1687 was calculated from the ratio of the peak heights.

[0129] (presence or absence of coarse particles) The presence or absence of coarse particles was measured for Film 1. Using a JEOL Ltd. scanning microscope JSM-6010PLUS / LA, secondary electron images were observed at an accelerating 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] (Gas barrier property evaluation: oxygen permeability) Oxygen transmission rate (OTR) was measured for Film 1, Laminate Film 2, and Laminate Film 3. According to JIS-K7126 (constant pressure method), measurements were performed using a Mocon oxygen transmission rate measuring device, OX-TRAN2 / 22, under an atmosphere of 23°C and 90% RH. RH stands for relative humidity. The unit of oxygen transmission rate is cc / day·atm·m2.

[0131] (Evaluation of hydrogen sulfide adsorption capacity) The hydrogen sulfide adsorption capacity was measured for laminate film 2. It 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 the gas concentration inside the bag was measured after a set time (10 minutes, 1 hour, 3 hours, 6 hours, and 24 hours) 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 the ability to adsorb hydrogen sulfide.

[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] [Table 1]

[0134] [Table 2]

[0135] [Table 3]

[0136] [Table 4]

[0137] [Table 5]

[0138] Examples 1 to 28 had good oxygen barrier properties under high humidity and / or after the bending test. On the other hand, Comparative Examples 1 to 3 had poorer oxygen barrier properties under high humidity and / or after the bending 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. The infrared absorption spectrum of the vapor-deposited layer (B) is 1575 m －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. 2. 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. 2. The gas barrier film according to claim 1, wherein the area of ​​particles of 20 nm or more in the vapor-deposited layer (B) is 1% or less of the film area.

5. 2. The 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. 2. 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 comprising the gas barrier film according to any one of claims 1 to 6.