Vapor deposition film, multilayer structure, packaging material, vacuum packaging bag, and vacuum adiabatic body

Abstract

Provided are: a vapor-deposited film which is suppressed in reduction in gas barrier properties after bending treatment and storage; and a multilayer structure, a packaging material, a vacuum packaging bag, and a vacuum adiabatic body which are obtained using the vapor-deposited film. A vapor-deposited film which comprises a resin barrier layer (A) and an aluminum vapor-deposited layer (B) that is directly laminated on the barrier layer (A) and has an average thickness of 30-100 nm (inclusive), the aluminum vapor-deposited layer (B) comprising an aluminum oxide layer (B1) and an aluminum layer (B2) in this order from the surface in contact with the barrier layer (A).

Description

Technical Field

[0001] The present invention relates to a vapor deposition film, a multilayer structure, a packaging material, a vacuum packaging bag, and a vacuum insulator. Background Art

[0002] A vapor deposition film in which a metal vapor deposition layer is provided on a resin-based substrate film is known. Such a vapor deposition film is used for various purposes such as a vacuum packaging bag for a vacuum insulator that requires gas barrier properties to maintain heat insulation performance, and a packaging material for protecting an article (such as food) that is easily deteriorated by oxygen. Patent Document 1 describes the following vapor deposition film, which is characterized in that it includes a substrate film containing a polyvinyl alcohol-based polymer and a metal vapor deposition layer laminated on the substrate film, and the average particle diameter of the metal vapor deposition layer measured by an electron microscope is 150 nm or less.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: International Publication No. 2013 / 125564 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] When producing a packaging material or the like having a specified shape from a vapor deposition film, a processing step including bending or the like is usually performed to complete the packaging material. In addition, the completed packaging material or the like may be bent during handling, use, or the like. However, the conventional vapor deposition film is insufficient in maintaining gas barrier properties under physical stress, particularly after bending. In addition, the conventional vapor deposition film has a tendency for the gas barrier property to decrease with long-term storage.

[0008] The present invention has been made based on such circumstances, and an object thereof is to provide a vapor deposition film in which a decrease in gas barrier properties after bending treatment and after storage is suppressed, and a multilayer structure, a packaging material, a vacuum packaging bag, and a vacuum insulator obtained by using such a vapor deposition film.

[0009] Means for Solving the Problems

[0010] The above object is achieved by providing the following technical solutions.

[0011] [1] A vapor deposition film having a resin-based barrier layer (A) and an aluminum vapor deposition layer (B), wherein the aluminum vapor deposition layer (B) is directly laminated on the barrier layer (A), has an average thickness of 30 nm or more and 100 nm or less, and the aluminum vapor deposition layer (B) continuously has an aluminum oxide layer (B1) and an aluminum layer (B2) in this order from the side in contact with the barrier layer (A). In the elemental analysis in the depth direction of the aluminum oxide layer (B1), the maximum value of the molar ratio of oxygen element to aluminum element (O / Al) measured by a scanning X-ray photoelectron spectroscopy apparatusMAX is 0.5 or more and 2.0 or less, and is the minimum value (O / Al) of the molar ratio of oxygen element to aluminum element measured by a scanning X-ray photoelectron spectroscopy analyzer in the depth direction analysis of the aluminum layer (B2). MIN is less than 0.5;

[0012] [2] The vapor deposition film according to [1], wherein the aluminum vapor deposition layer (B) has an aluminum oxide layer (B3), the aluminum oxide layer (B3) includes a surface (S) opposite to the surface in contact with the barrier layer (A), and in the elemental analysis of the surface (S), the molar ratio of oxygen element to aluminum element (O / Al) measured by a scanning X-ray photoelectron spectroscopy analyzer S is 0.5 or more and 2.0 or less;

[0013] [3] The vapor deposition film according to [1] or [2], wherein the barrier layer (A) contains at least one selected from ethylene alcohol-based polymers and polyester-based resins as a main component;

[0014] [4] The vapor deposition film according to any one of [1] to [3], wherein the barrier layer (A) is biaxially stretched;

[0015] [5] The vapor deposition film according to any one of [1] to [4], wherein the average thickness of the barrier layer (A) is 0.1 μm or more and 20 μm or less;

[0016] [6] The vapor deposition film according to any one of [1] to [5], wherein the average thickness of the aluminum vapor deposition layer (B) is 55 nm or more and 90 nm or less;

[0017] [7] The vapor deposition film according to any one of [1] to [6], which further has a polyolefin layer (D), and the polyolefin layer (D) is laminated on the surface of the barrier layer (A) opposite to the aluminum vapor deposition layer (B) via an adhesive resin layer (C);

[0018] [8] The vapor deposition film according to [7], wherein the barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are at least stretched along a uniaxial direction;

[0019] [9] A multilayer structure, which includes the vapor deposition film according to [7] or [8] and a polyolefin layer (E), and the polyolefin layer (E) is directly laminated or laminated via another layer on at least one surface of the above vapor deposition film;

[0020]

[10] The multilayer structure according to [9], wherein the polyolefin layers (E) are directly laminated or laminated via another layer on both surfaces of the above vapor deposition film, and each polyolefin layer (E) contains the same resin as a main component;

[0021]

[11] A multilayer structure according to [9] or

[10] , wherein the thickness ratio of the barrier layer (A) to the total thickness of the multilayer structure is 5% or less;

[0022]

[12] A multilayer structure comprising the vapor deposition film according to any one of [1] to [6] and a polyolefin layer (E), which is directly laminated or laminated via other layers on the vapor deposition film;

[0023]

[13] A multilayer structure according to

[12] , further comprising another vapor deposition film, which is directly laminated or laminated via other layers on the vapor deposition film, the other vapor deposition film having a resin barrier layer (a) and an aluminum vapor deposition layer (b), the aluminum vapor deposition layer (b) being directly laminated on the barrier layer (a) and having an average thickness of 30 nm or more and 100 nm or less;

[0024]

[14] A multilayer structure according to

[13] , wherein the aluminum vapor deposition layer (b) successively and continuously has an aluminum oxide layer (b1) and an aluminum layer (b2) from the side in contact with the barrier layer (a), and in the elemental analysis in the depth direction of the aluminum oxide layer (b1), the maximum value of the molar ratio of oxygen element to aluminum element (O / Al) MAX measured by a scanning X-ray photoelectron spectroscopy apparatus is 0.5 or more and 2.0 or less, and in the depth direction analysis of the aluminum layer (b2), the minimum value of the molar ratio of oxygen element to aluminum element (O / Al) MIN is less than 0.5;

[0025]

[15] A multilayer structure according to any one of

[12] to

[14] , further comprising a polyamide layer (F), which is directly laminated or laminated via other layers on the vapor deposition film;

[0026]

[16] A packaging material comprising the vapor deposition film according to any one of [1] to [8] or the multilayer structure according to any one of [9] to

[15] ;

[0027]

[17] A vacuum packaging bag comprising a packaging bag formed of the packaging material according to

[16] , and the inside of the packaging bag is decompressed;

[0028]

[18] A vacuum insulator comprising: the vacuum packaging bag according to

[17] ; and a core material disposed inside the vacuum packaging bag.

[0029] Advantages of the Invention

[0030] According to the present invention, there can be provided a vapor deposition film in which a decrease in gas barrier properties after bending treatment and storage is suppressed, and a multilayer structure, a packaging material, a vacuum packaging bag, and a vacuum insulator obtained using such a vapor deposition film. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic cross-sectional view of the vapor deposition film according to an embodiment of the present invention. Detailed Description of the Invention

[0032] In this specification, "gas barrier property" mainly refers to oxygen barrier property. Sometimes, the property in which the decrease in gas barrier property after bending treatment is suppressed is expressed as "flex resistance". In addition, sometimes, the property in which the decrease in gas barrier property after storage is suppressed is expressed as "storage property".

[0033] "Main component" means the component having the largest content based on mass basis.

[0034] "Average thickness" means the average value of the thicknesses measured at any five places.

[0035] In addition, when showing the layer constitution in this specification, " / " means direct lamination, and " / / " means direct lamination or lamination with the aid of an adhesive layer.

[0036] "Outermost layer" means: when distinguishing between the surface and the inside, it is not limited to the layer existing on the surface side. That is, a vapor deposition film or a multilayer structure composed of two or more layers has two outermost layers, one on one side and the other on the other side. In addition, in the case of a structure in which the inside and the outside are distinguished, such as a bag shape or a container shape, sometimes the outermost layer on the inside is also called the innermost layer, and the outermost layer on the outside is called the outermost layer.

[0037] <Vapor Deposition Film>

[0038] The vapor deposition film of the present invention has a resin barrier layer (A) and an aluminum vapor deposition layer (B), the aluminum vapor deposition layer (B) is directly laminated on the barrier layer (A), the average thickness is 30 nm or more and 100 nm or less, and the aluminum vapor deposition layer (B) successively and continuously has an aluminum oxide layer (B1) and an aluminum layer (B2) from the side in contact with the barrier layer (A). In the elemental analysis in the depth direction of the aluminum oxide layer (B1), the maximum value (O / Al) of the molar ratio of oxygen element to aluminum element measured by a scanning X-ray photoelectron spectroscopy device MAX is 0.5 or more and 2.0 or less, and in the depth direction analysis of the aluminum layer (B2), the minimum value (O / Al) of the molar ratio of oxygen element to aluminum element measured by a scanning X-ray photoelectron spectroscopy device MIN is less than 0.5.

[0039] The vapor deposition film of the present invention has excellent bend resistance and storage stability. The reason for this is not yet certain, but it is presumably due to the following reasons. In this vapor deposition film, by making the region of the aluminum vapor deposition layer (B) in contact with the barrier layer (A) an aluminum oxide layer (B1), the adhesion strength between the barrier layer (A) and the aluminum vapor deposition layer (B) is increased. As a result, even when bending treatment is performed or dimensional changes occur during storage, the state in which the aluminum vapor deposition layer (B) and the barrier layer (A) are firmly adhered is maintained. Therefore, it is presumed that in this vapor deposition film, the decrease in gas barrier properties after bending treatment and storage is suppressed. In addition, when using this vapor deposition film to package foods, etc. and store them, the decrease in the adhesion between the barrier layer (A) and the aluminum vapor deposition layer (B) caused by components contained in the food contents, etc. is also suppressed. The part where the aluminum vapor deposition layer (B) peels off from the barrier layer (A) turns white, resulting in a reduction in appearance. Therefore, the decrease in gas barrier properties of the packaging material obtained using this vapor deposition film after storage is suppressed, and the reduction in appearance is also suppressed. Furthermore, when using this vapor deposition film to package foods, etc. and store them, it is possible to suppress whitening caused by the rapid oxidation of the aluminum vapor deposition layer (B) caused by components contained in the food contents, etc., transparency, and the decrease in gas barrier properties caused by the corrosion of the aluminum oxide layer (B1). By the presence of the aluminum oxide layer (B1) oxidized at a specific ratio, the rapid oxidation of the aluminum layer (B2) and the corrosion of the aluminum oxide layer (B1) can be suppressed. Therefore, the decrease in gas barrier properties after storage is suppressed, and the reduction in appearance is also suppressed.

[0040] (Barrier layer (A))

[0041] The barrier layer (A) is a resin layer. The barrier layer (A) can be a base layer for the aluminum vapor deposition layer (B) formed by vapor deposition. The barrier layer (A) can be a layer mainly composed of resin. The resin constituting the barrier layer (A) is preferably a thermoplastic resin.

[0042] Regarding the resin as the main component of the barrier layer (A), a resin with high gas barrier properties is preferably used. For example, when producing an unstretched film composed only of resin, it is preferred that the oxygen permeability of the film is 100 mL·20 μm / (m 2 ·day·atm) or less, more preferably 50 mL·20 μm / (m 2 ·day·atm) or less, and even more preferably 10 mL·20 μm / (m 2 ·day·atm) or less. Here, the oxygen permeability is a value measured according to the method described in ISO14663-2Annex C (1999) under the conditions of 20°C and 65% RH. For example, the oxygen permeability of "50 mL·20 μm / (m 2 ·day·atm)" means that when the average thickness is converted to 20 μm, based on a film of 1 m 2, with a pressure difference of 1 atmospheric pressure of oxygen, 50 mL of oxygen permeates through per day.

[0043] Examples of the resin that is the main component of the barrier layer (A) include ethylene alcohol-based polymers, polyester-based resins, polyamides, polyvinylidene chloride, acrylonitrile copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. Preferably, it is at least one selected from ethylene alcohol-based polymers and polyester-based resins, and more preferably an ethylene alcohol-based polymer. By using such a resin as the main component of the barrier layer (A), the gas barrier property is improved, and in addition, the decrease in the gas barrier property after bending treatment and storage is further suppressed. One kind or two or more kinds of resins constituting the barrier layer (A) can be used.

[0044] The polyester-based resin refers to a polymer having an ester bond. The polyester-based resin can be obtained by polycondensation of a polycarboxylic acid and a polyol. Examples of the polyester-based resin include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyglycolic acid (PGA), aromatic liquid crystal polyester, etc., and PET is preferred.

[0045] The ethylene alcohol-based polymer refers to a polymer having an ethylene alcohol unit. The ethylene alcohol-based polymer can be obtained, for example, by saponifying a vinyl ester homopolymer or a copolymer of a vinyl ester and other monomers using an alkali catalyst, etc. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate, etc., and vinyl acetate is preferred. Examples of other monomers include ethylene; α-olefins such as propylene, butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.; unsaturated carboxylic acids or their esters such as (meth)acrylic acid; vinyl silane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or their salts; vinyl pyrrolidone compounds such as N-vinylpyrrolidone, etc. Among these, ethylene is preferred.

[0046] The production of the ethylene alcohol-based polymer can be carried out by a known method. A chain transfer agent can be used during production. Examples of the chain transfer agent include alkyl mercaptans, etc.

[0047] As the saponification degree of the ethylene alcohol-based polymer (the ratio (mol%) of the ethylene alcohol unit to the total of the ethylene alcohol unit and the vinyl ester unit), it is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more. By making the saponification degree above the above upper limit, there is a tendency for the gas barrier property of the vapor deposition film to be improved under high humidity. The upper limit of the saponification degree of the ethylene alcohol-based polymer can be 100 mol%. The saponification degree of the ethylene alcohol-based polymer can be determined by nuclear magnetic resonance (NMR) method.

[0048] The content of the vinyl alcohol unit in the vinyl alcohol-based polymer relative to all structural units is preferably 30 mol% or more and 100 mol% or less, more preferably 35 mol% or more and 90 mol% or more, further preferably 40 mol% or more and 80 mol% or less, and even more preferably 45 mol% or more and 75 mol% or less.

[0049] As the vinyl alcohol-based polymer, an ethylene-vinyl alcohol copolymer (hereinafter also referred to as "EVOH") is preferred. The content of the ethylene unit in EVOH relative to all structural units is preferably 10 mol% or more and 65 mol% or less, preferably 20 mol% or more and 60 mol%, and further preferably 25 mol% or more and 55 mol% or less.

[0050] EVOH may have other structural units in addition to the vinyl alcohol unit, the ethylene unit, and the vinyl ester unit. When EVOH has other structural units, the content of the above other structural units relative to all structural units of EVOH is sometimes preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, even more preferably 5 mol% or less, and particularly preferably 1 mol% or less. In addition, when EVOH has the above other structural units, the content can be 0.05 mol% or more and can be 0.1 mol% or more.

[0051] As the MFR (190 °C, 2.16 kg load) of EVOH, it is preferably 0.5 g / 10 min or more and 12 g / 10 min or less, more preferably 1.0 g / 10 min or more and 8.0 g / min or less.

[0052] The lower limit of the content of the resin in the barrier layer (A) is preferably 70% by mass, more preferably 80% by mass, further preferably 90% by mass, and can be 95% by mass, 99% by mass, or 99.9% by mass from the viewpoints of gas barrier properties and the like. The upper limit of the content of the resin in the barrier layer (A) can be 100% by mass and can be 99.99% by mass.

[0053] The barrier layer (A) may contain inorganic oxide particles. The inorganic oxide constituting the inorganic oxide particles is not particularly limited, and examples thereof include silica, alumina, magnesia, zirconia, ceria, tungsten oxide, molybdenum oxide, and their composites. Among these, silica or silica-magnesia is preferred, and silica is more preferred.

[0054] As the lower limit of the content of the inorganic oxide particles in the barrier layer (A), it is preferably 0.001% by mass, more preferably 0.005% by mass, and still more preferably 0.01% by mass. In addition, as the upper limit of the content of the inorganic oxide particles, it is preferably 1% by mass, more preferably 0.7% by mass, and still more preferably 0.5% by mass. By making the content of the inorganic oxide particles within the above range, there is a tendency for the gas barrier property to be further improved.

[0055] As the average particle diameter of the inorganic oxide particles, it is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 5 μm or less. By making the average particle diameter of the inorganic oxide particles within the above range, there is a tendency for the gas barrier property to be further improved. The average particle diameter of the inorganic oxide particles is set to the value measured by the laser diffraction scattering method.

[0056] In addition to this, the barrier layer (A) may contain a boron compound, a carboxylic acid, a phosphorus compound, a metal ion, an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a colorant, a filler, a heat stabilizer, etc. The barrier layer (A) may contain two or more of these optional components.

[0057] The barrier layer (A) may be an unstretched layer or a stretched layer. The barrier layer (A) may be uniaxially stretched or biaxially stretched. When the barrier layer (A) is a stretched layer, especially when it is a biaxially stretched layer, even a thin barrier layer (A) can exhibit good gas barrier properties.

[0058] When the barrier layer (A) is a stretched layer, for example, it is preferably stretched at least 2 times or more and less than 12 times along at least one uniaxial direction, more preferably stretched at least 3 times or more and less than 6 times along at least one uniaxial direction. In addition, the barrier layer (A) is also preferably stretched 2 times or more and less than 12 times along the biaxial directions respectively, and more preferably stretched 3 times or more and less than 6 times along the biaxial directions respectively.

[0059] As the lower limit of the average thickness of the barrier layer (A), it is preferably 0.1 μm, more preferably 0.5 μm, still more preferably 1 μm, and may be 2 μm, 4 μm or 6 μm. By making the average thickness of the barrier layer (A) above the above lower limit, the gas barrier property and the like can be improved. As the upper limit of the average thickness of the barrier layer (A), it is preferably 20 μm, more preferably 15 μm, and may be 10 μm, 5 μm, 3 μm or 2 μm. By making the average thickness of the barrier layer (A) below the above upper limit, the thinning and lightening of the vapor deposition film and the like can be achieved.

[0060] As the oxygen permeability of the barrier layer (A), it is preferably 50 mL·20 μm / (m 2 ·day·atm) or less, more preferably 10 mL·20 μm / (m2 ·day·atm) or less, more preferably 5 mL·20 μm / (m 2 ·day·atm) or less, particularly preferably 1 mL·20 μm / (m 2 ·day·atm) or less. Here, the oxygen permeability is a value measured according to the method described in ISO 14663-2 Annex C (1999) under the conditions of 20°C and 65% RH.

[0061] The barrier layer (A) may be composed of a single layer or multiple layers.

[0062] The barrier layer (A) may use a resin film. As a method for manufacturing the resin film having the barrier layer (A), there is no particular limitation, and examples include a melting method, a solution method, a calendering method, etc. Among these, the melting method is preferred. As the melting method, a casting method and a blown film method can be cited, and among these, the casting method is preferred. In addition, a stretched film stretched by a known method may also be used.

[0063] (Aluminum vapor deposition layer (B))

[0064] The aluminum vapor deposition layer (B) is a layer directly laminated on the surface of the barrier layer (A) by vapor deposition. By providing the aluminum vapor deposition layer (B) on the vapor deposition film, good gas barrier properties can be exhibited.

[0065] The aluminum vapor deposition layer (B) successively has an aluminum oxide layer (B1) and an aluminum layer (B2) continuously from the side in contact with the barrier layer (A). The aluminum vapor deposition layer (B) preferably further has an aluminum oxide layer (B3) that includes the surface (S) opposite to the side in contact with the barrier layer (A).

[0066] Figure 1 shows the vapor deposition film 10 according to an embodiment of the present invention. The vapor deposition film 10 has a resinous barrier layer (A) and an aluminum vapor deposition layer (B) directly laminated on the barrier layer (A). The aluminum vapor deposition layer (B) has a three-layer structure of an aluminum oxide layer (B1), an aluminum layer (B2), and an aluminum oxide layer (B3) successively from the side in contact with the barrier layer (A). The vapor deposition film of the present invention is not limited to Figure 1 the structure of the vapor deposition film 10 having such a structure. The vapor deposition film of the present invention may have an adhesive resin layer (C), a polyolefin layer (D), and other layers described later. In addition, it may have other layers covering the surface (S) opposite to the surface of the aluminum vapor deposition layer (B) in contact with the barrier layer (A). As Figure 1 in the vapor deposition film 10, the surface (S) of the aluminum vapor deposition layer (B) may be uncovered, that is, exposed.

[0067] As other layers covering the face (S), a top coat layer can be cited, for example. The top coat layer can be provided by coating a solution containing a solvent-soluble or water-soluble resin (such as polyester resin, acrylic resin, vinyl alcohol resin, ethylene vinyl alcohol copolymer (EVOH) resin, vinyl-modified resin, epoxy resin, resin containing oxazoline group, modified styrene resin, modified silicone resin, alkyl titanate, etc.). The top coat layer can also add fillers to improve barrier properties, abrasion resistance, smoothness, etc. As fillers, silica sol, alumina sol, particulate inorganic fillers, layered inorganic fillers, etc. can be cited, for example. The top coat layer is preferably formed by adding fillers to the aforementioned resin and polymerizing or condensing it. As other layers covering the face (S), it can be a thermoplastic resin layer formed by a method other than solution coating, each layer used in other multilayer structures described later, etc.

[0068] There is no clear interface between the alumina layer (B1) and the aluminum layer (B2), and between the aluminum layer (B2) and the alumina layer (B3). In addition, in each of the alumina layer (B1), the aluminum layer (B2), and the alumina layer (B3), the elemental composition is not usually constant. Starting from the alumina layer (B1) and towards the aluminum layer (B2), the content ratio of oxygen element gradually decreases. In addition, starting from the aluminum layer (B2) and towards the alumina layer (B3), the content ratio of oxygen element gradually increases. In other words, in the aluminum vapor deposition layer (B), the content ratio of oxygen element in the intermediate layer part (aluminum layer (B2)) is relatively low. And in the aluminum vapor deposition layer (B), in the region with a specified thickness starting from the face in contact with the barrier layer (A) (alumina layer (B1)), and in the region with a specified thickness starting from the face opposite to the face in contact with the barrier layer (A) (face (S)) (alumina layer (B3)), the content ratio of oxygen element is relatively higher compared to the intermediate layer part (aluminum layer (B2)).

[0069] In the elemental analysis in the depth direction of the alumina layer (B1), the maximum molar ratio of oxygen element to aluminum element (O / Al) measured by a scanning X-ray photoelectron spectroscopy apparatus MAX is 0.5 or more and 2.0 or less, preferably 0.8 or more and 1.8 or less, more preferably 1.1 or more and 1.5 or less. By making the maximum molar ratio of oxygen element to aluminum element (O / Al) in the alumina layer (B1) MAX be in the above range, the adhesion of the aluminum vapor deposition layer (B) to the barrier layer (A) is improved, and the bending resistance and storage stability of the vapor deposition film can be improved.

[0070] In the elemental analysis in the depth direction of the alumina layer (B1), the maximum molar ratio of oxygen element to aluminum element (O / Al) is observed MAXThe position preferably exists in the range of 0 nm or more and 20 nm or less from the surface in contact with the barrier layer (A), more preferably in the range of 0 nm or more and 15 nm or less.

[0071] In the depth direction analysis of the aluminum layer (B2), the minimum value of the molar ratio of oxygen element to aluminum element (O / Al) measured by a scanning X-ray photoelectron spectroscopy apparatus MIN is less than 0.5, preferably 0.001 or more and less than 0.5, more preferably 0.003 or more and less than 0.2, further preferably 0.005 or more and less than 0.10, and even more preferably 0.01 or more and less than 0.06. By making the minimum value of the molar ratio of oxygen element (O) to aluminum element (Al) in the aluminum layer (B2) (O / Al) MIN fall within the above range, there is a tendency for the gas barrier property, bend resistance, storage property, etc. of the vapor deposition film to be improved.

[0072] In the elemental analysis of the surface (S) on the opposite side of the surface of the aluminum vapor deposition layer (B) in contact with the barrier layer (A), the molar ratio of oxygen element to aluminum element (O / Al) measured by a scanning X-ray photoelectron spectroscopy apparatus S is preferably 0.5 or more and 2.0 or less, more preferably 0.8 or more and 1.8 or less, and further preferably 1.1 or more and 1.7 or less. By making the molar ratio of oxygen element to aluminum element (O / Al) on the surface (S) of the aluminum vapor deposition layer (B) S fall within the above range, there is a tendency for the bend resistance, storage property, etc. to be further improved.

[0073] Regarding the maximum value of the molar ratio of oxygen element to aluminum element (O / Al) in the aluminum oxide layer (B1) MAX and the molar ratio of oxygen element to aluminum element (O / Al) on the surface (S) of the aluminum vapor deposition layer (B) S , either value can be larger. That is, the maximum value of the molar ratio of oxygen element to aluminum element (O / Al) in the aluminum oxide layer (B1) MAX is the maximum value of the aluminum oxide layer (B1) and does not necessarily coincide with the maximum value of the aluminum vapor deposition layer (B). In addition, in the part of the aluminum oxide layer (B3) other than the surface (S), there may be a part where the molar ratio of oxygen element to aluminum element (O / Al) is higher than the value of (O / Al) MAX or (O / Al) S .

[0074] The average thickness of the aluminum vapor deposition layer (B) is 30 nm or more and 100 nm or less. The lower limit of the average thickness of the aluminum vapor deposition layer (B) is preferably 35 nm, more preferably 45 nm, further preferably 55 nm, and even more preferably 65 nm. By making the average thickness of the aluminum vapor deposition layer (B) above the above lower limit, the gas barrier property, bend resistance, storage property, etc. of the vapor deposition film can be further improved. The upper limit of the average thickness of the aluminum vapor deposition layer (B) is preferably 90 nm, and can be 80 nm, 70 nm, or 60 nm.

[0075] The aluminum vapor deposition layer (B) can be effectively provided by, for example, vacuum vapor deposition. For example, when vacuum vapor depositing aluminum on a resin film that becomes the barrier layer (A) while transporting the resin film, oxygen is supplied in a small amount toward the resin film in front of the surface to be vapor deposited while vapor deposition is performed. Thereby, aluminum elements are laminated in the form of aluminum oxide on the surface of the resin film (barrier layer (A)), and an aluminum oxide layer (B1) is formed. The maximum value (O / Al) of the molar ratio of oxygen element (O) to aluminum element (Al) in the aluminum oxide layer (B1) MAX can be controlled according to the supply amount of oxygen blown onto the resin film, etc. As the amount of oxygen supplied to the resin film, it can be set to, for example, 20 mL / min or more and 180 mL / min. By supplying oxygen, the pressure during vacuum vapor deposition is reduced. It is preferred that the pressure during vacuum vapor deposition be 1.0×10 -4 Pa or more and 1.0×10 -3 Pa or less when supplying oxygen. Among them, according to the vapor deposition rate of aluminum, etc., the appropriate oxygen supply amount and pressure are adjusted as appropriate.

[0076] It should be noted that the vapor deposition film provided with the aluminum vapor deposition layer (B) by vacuum vapor deposition usually forms an oxidation coating film on the surface by being exposed to an air atmosphere, etc., and this oxidation coating film can become the aluminum oxide layer (B3). In addition, the aluminum vapor deposition layer (B) can be provided by vapor deposition methods other than the above. The aluminum vapor deposition layer (B) can be provided by sputtering, ion plating, ion beam mixing, plasma CVD, laser CVD, MO-CVD, thermal CVD, etc.

[0077] Before performing vapor deposition, the surface of the barrier layer (A) to be vapor deposited can be subjected to plasma treatment. The plasma treatment can use a known method, and atmospheric pressure plasma treatment is preferred. As the discharge gas in the atmospheric pressure plasma treatment, for example, nitrogen, helium, neon, argon, krypton, xenon, radon, etc. can be cited.

[0078] (Adhesive resin layer (C))

[0079] The vapor deposition film of the present invention preferably further has a polyolefin layer (D), and the polyolefin layer (D) is laminated on the surface of the barrier layer (A) opposite to the aluminum vapor deposition layer (B) via the adhesive resin layer (C).

[0080] The adhesive resin layer (C) usually contains an adhesive resin as the main component. As the adhesive resin, there is no particular limitation as long as it is a resin having adhesiveness, and examples thereof include acid-modified polyolefins (carboxylic acid-modified polyolefins, sulfonic acid-modified polyolefins, etc.), epoxy-modified polyolefins, etc. The adhesive resin is preferably a thermoplastic resin. The adhesive resin is preferably an acid-modified polyolefin (acid-modified polyethylene, acid-modified polypropylene, etc.), more preferably acid-modified polyethylene. In addition, the adhesive resin is also preferably a carboxylic acid-modified polyolefin, more preferably carboxylic acid-modified polyethylene.

[0081] The carboxylic acid-modified polyolefin may be a polyolefin having a carboxyl group or its anhydride group. The carboxylic acid-modified polyolefin (polyolefin having a carboxyl group or its anhydride group) can be obtained, for example, by chemically bonding an ethylenically unsaturated carboxylic acid or its anhydride to an unmodified polyolefin by an addition reaction, a graft reaction, or the like.

[0082] As the unmodified polyolefin used for manufacturing the carboxylic acid-modified polyolefin, polyethylene or polypropylene is preferred, and polyethylene is more preferred.

[0083] Examples of the ethylenically unsaturated carboxylic acid and its anhydride include monocarboxylic acids, monocarboxylic acid esters, dicarboxylic acids, dicarboxylic acid monoesters, dicarboxylic acid diesters, dicarboxylic acid anhydrides, etc. Specifically, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, etc. may be mentioned. Among these, dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride are preferred, and maleic anhydride is more preferred. That is, the adhesive resin is also preferably a maleic anhydride-modified polyolefin, more preferably a maleic anhydride-modified polyethylene.

[0084] The carboxylic acid-modified polyolefin is obtained, for example, by introducing an ethylenically unsaturated carboxylic acid or its anhydride into an unmodified polyolefin by an addition reaction or a graft reaction in the presence of a solvent such as xylene and a catalyst such as a peroxide. As the lower limit of the addition amount or graft amount (modification degree) of the carboxylic acid or its anhydride on the unmodified polyolefin, it is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, relative to the unmodified polyolefin. On the other hand, as the upper limit of the above addition amount or graft amount (modification degree), it is preferably 15% by mass or less, more preferably 10% by mass or less, relative to the unmodified polyolefin.

[0085] As the content of the adhesive resin in the adhesive resin layer (C), it is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, still more preferably 97% by mass or more and 100% by mass or less. In the adhesive resin layer (C), as components other than the adhesive resin, it may contain other resins such as antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, and adhesive resins, etc., in addition to the adhesive resin.

[0086] The adhesive resin layer (C) may be an unstretched layer or a stretched layer.

[0087] As the lower limit of the average thickness of the adhesive resin layer (C), it is preferably 0.1 μm, more preferably 0.5 μm, still more preferably 1 μm, and may be 2 μm. By making the average thickness of the adhesive resin layer (C) above the above lower limit, sufficient adhesiveness and the like can be exhibited. As the upper limit of the average thickness of the adhesive resin layer (C), it is preferably 20 μm, more preferably 10 μm, still more preferably 5 μm, and may be 3 μm. By making the average thickness of the adhesive resin layer (C) below the above upper limit, thinning of the vapor deposition film and the like can be achieved.

[0088] (Polyolefin layer (D))

[0089] When the vapor deposition film has a polyolefin layer (D), water vapor barrier properties, bend resistance, storage properties, etc. can be improved. In addition, when the polyolefin layer (D) is the vapor deposition film of the outermost layer, by, for example, using the polyolefin layer (D) as a heat-sealable layer for heat sealing, etc., it can also be easily formed into a shape such as a bag shape. In the vapor deposition film of the present invention, when formed into a bag shape, the layer that becomes the innermost layer may be the polyolefin layer (D).

[0090] The polyolefin layer (D) contains polyolefin as the main component. Examples of the polyolefin include homopolymers or copolymers of olefins such as polyethylene (linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc.), ethylene-propylene copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene, and polyisopentene. Among these, polyethylene or polypropylene is preferred, and polypropylene is more preferred. One or more kinds of polyolefins can be used.

[0091] As the content of the polyolefin in the polyolefin layer (D), it is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, still more preferably 97% by mass or more and 100% by mass or less. In the polyolefin layer (D), as components other than the polyolefin, an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a colorant, a filler, a heat stabilizer, other resins other than the polyolefin, etc. may be contained.

[0092] The polyolefin layer (D) may be an unstretched layer or a stretched layer.

[0093] As the lower limit of the average thickness of the polyolefin layer (D), it is preferably 1 μm, more preferably 5 μm, and still more preferably 10 μm. By making the average thickness of the polyolefin layer (D) above the above lower limit, sufficient moisture resistance and the like can be exhibited. As the upper limit of the average thickness of the polyolefin layer (D), it is preferably 100 μm, more preferably 50 μm, and still more preferably 30 μm. By making the average thickness of the polyolefin layer (D) below the above upper limit, thinning of the vapor deposition film and the like can be achieved.

[0094] The polyolefin layer (D) may be composed of a single layer or multiple layers.

[0095] The barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are preferably stretched at least uniaxially, and more preferably stretched biaxially. In this case, the gas barrier property, bending resistance, storage property, etc. of the vapor deposition film can be further improved. The barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are preferably stretched, for example, at least 2 times or more and less than 12 times uniaxially, and more preferably at least 3 times or more and less than 6 times uniaxially. In addition, the barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are also preferably stretched 2 times or more and less than 12 times respectively biaxially, and more preferably stretched 3 times or more and less than 6 times respectively biaxially.

[0096] The barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are preferably integrated and stretched. For example, a multilayer film in which the barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are laminated in sequence can be formed and stretched. In addition, by vapor depositing an aluminum vapor deposition layer (B) on the side surface of the barrier layer (A) of a multilayer film in which the barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are laminated in sequence, a vapor deposition film can be obtained.

[0097] As a method for manufacturing a multilayer film having a barrier layer (A), an adhesive resin layer (C), and a polyolefin layer (D), there is no particular limitation, and a coextrusion method is preferred. By adopting the coextrusion method, film properties such as gas barrier property and flexibility, process qualification (reduction of film thickness unevenness), and economy (easy to achieve the target composition (such as thinning of the barrier layer (A) etc.) with fewer processes) can be balanced at a high level. That is, the barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are preferably coextrusion films. Examples of the coextrusion method include coextrusion casting, coextrusion blow molding, coextrusion coating molding, etc.

[0098] The vapor deposition film of the present invention may have other layers in addition to the barrier layer (A), aluminum vapor deposition layer (B), adhesive resin layer (C), and polyolefin layer (D). As the other layers, the above-mentioned top coat layer, other thermoplastic resin layers, other vapor deposition layers, paper layers, metal foil layers, etc. may be mentioned. The other layers may be only one kind, or two or more kinds.

[0099] (Layer structure, etc.)

[0100] As the layer structure of the vapor deposition film of the present invention, for example, the following may be mentioned:

[0101] (1) A / B,

[0102] (2) D / C / A / B,

[0103] (3) X / / D / C / A / B,

[0104] (4) A / B / / X,

[0105] (5) D / C / A / B / / X,

[0106] (6) X / / D / C / A / B / / X, etc.

[0107] It should be noted that A is the barrier layer, B is the aluminum vapor deposition layer, C is the adhesive resin layer, D is the polyolefin layer, and X is the other layer.

[0108] The average thickness of the vapor deposition film of the present invention is not particularly limited. For example, the lower limit may be 5 μm, 10 μm, or 15 μm. On the other hand, the upper limit of the average thickness may be 200 μm, 100 μm, 50 μm, 30 μm, or 20 μm. The shape of the vapor deposition film is not particularly limited as long as it has a laminated structure.

[0109] The oxygen permeability of the vapor deposition film of the present invention is preferably less than 1.0 mL / (m 2 ·day·atm), more preferably less than 0.10 mL / (m 2 ·day·atm), still more preferably less than 0.05 mL / (m 2 ·day·atm), and particularly preferably less than 0.01 mL / (m 2 ·day·atm). By making the oxygen permeability less than the above upper limit, it can be particularly suitably used as various packaging materials, etc. On the other hand, the lower limit of the oxygen permeability may be 0 mL / (m 2 ·day·atm), and may be 0.001 mL / (m 2 ·day·atm). The oxygen permeability of the vapor deposition film is a value measured according to the method described in ISO 14663-2 Annex C (1999) under the conditions of 20 °C and 65% RH.

[0110] The vapor deposition film of the present invention has excellent bend resistance and storage properties. In addition, the vapor deposition film also has good gas barrier properties. Therefore, the vapor deposition film can be applied to various uses. As uses of the vapor deposition film, various packaging materials such as food packaging, chemical packaging, industrial drug packaging, pesticide packaging, etc., and vacuum insulation bags can be cited.

[0111] <Multilayer structure>

[0112] The vapor deposition film of the present invention can also be suitably used as a multilayer structure further laminated with other layers.

[0113] (Polyolefin layer (E))

[0114] The multilayer structure according to one embodiment of the present invention includes the vapor deposition film of the present invention and a polyolefin layer (E), and the polyolefin layer (E) is directly laminated or laminated on at least one surface of the vapor deposition film through other layers. When the multilayer structure simultaneously includes a vapor deposition film and a polyolefin layer (E), it is possible to improve the water vapor barrier property, etc. on the basis of improving the gas barrier property. In addition, in the case of a multilayer structure in which the polyolefin layer (E) is the outermost layer, for example, by using the polyolefin layer (E) as a heat-sealing layer for heat sealing, etc., it is also possible to easily form a shape such as a bag shape. In the multilayer structure of the present invention, when formed into a bag shape, the layer that becomes the innermost layer can be the polyolefin layer (E).

[0115] When the vapor deposition film included in the multilayer structure of the present invention has a polyolefin layer (D), the polyolefin layer (D) is one of the coextruded films, and can be distinguished because the polyolefin layer (E) is a layer laminated separately by, for example, extrusion lamination, etc. However, the lamination method of the polyolefin layer (E) is not particularly limited.

[0116] The polyolefin layer (E) can be directly laminated on the vapor deposition film of the present invention, or can be laminated through other layers.

[0117] As other layers, an adhesive layer, etc. can be cited. As the adhesive layer, a layer obtained by using the same adhesive resin as the above-mentioned adhesive resin layer (C), a layer formed by a curable adhesive (two-component reaction type polyurethane adhesive, etc.), etc. can be cited.

[0118] The specific form of the composition of the polyolefin layer (E) is the same as that of the polyolefin layer (D). Regarding the polyolefin as the main component of the polyolefin layer (E), polyethylene or polypropylene is preferred.

[0119] The polyolefin layer (E) can be an unstretched layer or a stretched layer. In the multilayer structure of the present invention, when formed into a bag shape, when the innermost layer is the polyolefin layer (E), from the viewpoint of good heat sealability, the innermost polyolefin layer (E) is preferably an unstretched layer. In the multilayer structure of the present invention, when formed into a bag shape, when the outermost layer is the polyolefin layer (E), from the viewpoint of good mechanical strength, the outermost polyolefin (E) is preferably stretched, and more preferably biaxially stretched.

[0120] As the lower limit of the average thickness of the polyolefin layer (E), it is preferably 5 μm, more preferably 10 μm, further preferably 15 μm, and can be 20 μm, 30 μm or 40 μm. By making the average thickness of the polyolefin layer (E) above the above lower limit, sufficient moisture resistance and the like can be exhibited. In addition, when the polyolefin layer (E) is the outermost layer, by making the average thickness of the polyolefin layer (E) above the above lower limit, sufficient heat sealability can also be exhibited. As the upper limit of the average thickness of the polyolefin layer (E), it is preferably 200 μm, more preferably 100 μm, can be 60 μm, and can also be 40 μm. By making the average thickness of the polyolefin layer (E) below the above upper limit, thinning of the multilayer structure and the like can be achieved.

[0121] When the polyolefin layer (E) is laminated on the polyolefin layer (D), from the viewpoint of suppressing the decrease in gas barrier properties after storage, the total thickness of the polyolefin layer (D) and the polyolefin layer (E) is preferably 40 μm or more, more preferably 50 μm or more, further preferably 55 μm or more, and particularly preferably 60 μm or more. The total thickness of the polyolefin layer (D) and the polyolefin layer (E) can be, for example, 200 μm or less.

[0122] The polyolefin layer (E) can be composed of a single layer or multiple layers.

[0123] In the multilayer structure of the present invention, the polyolefin layer (E) can be directly laminated or laminated via other layers on both sides of the vapor deposition film of the present invention. In this form of multilayer structure, each polyolefin layer (E) is sometimes preferably the outermost layer.

[0124] When the polyolefin layer (E) is directly laminated or laminated via other layers on both sides of the vapor deposition film of the present invention, each polyolefin layer (E) preferably contains the same resin as the main component. The same resin means, for example, all are polyethylene, all are polypropylene, etc. Among the same resins, the density, melting point, presence or absence of stretching, etc. can be different. For example, the same material can be used to laminate two polyolefin layers (E). When the two polyolefin layers (E) contain the same resin as the main component, there are advantages such as improved recyclability. For example, when recycled and melt-molded, the compatibility is excellent, and a recycled product with excellent appearance can be molded.

[0125] (Other vapor deposition film)

[0126] The multilayer structure of the present invention may further include other vapor deposition films (second vapor deposition films), and the other vapor deposition films (second vapor deposition films) are directly laminated or laminated on the vapor deposition film (first vapor deposition film) of the present invention via other layers. In other words, the multilayer structure of the present invention may include a plurality of vapor deposition films, and at least one of the plurality of vapor deposition films is the vapor deposition film of the present invention. The gas barrier property, bend resistance, storage property, etc. of the multilayer structure having a plurality of vapor deposition films are more excellent.

[0127] The plurality of vapor deposition films may be directly laminated to each other or laminated via other layers. Examples of the other layers include an adhesive layer, a polyolefin layer (E), a polyamide layer (F) described later, etc., and an adhesive layer is preferred. A plurality of layers may exist between the plurality of vapor deposition films.

[0128] The other vapor deposition film (second vapor deposition film) has, for example, a resinous barrier layer (a) and an aluminum vapor deposition layer (b), and the aluminum vapor deposition layer (b) is directly laminated on the barrier layer (a) and has an average thickness of 30 nm or more and 100 nm or less. The specific form and suitable form of the barrier layer (a) and the aluminum vapor deposition layer (b) are the same as the specific form and suitable form of the barrier layer (A) and the aluminum vapor deposition layer (B) of the vapor deposition film of the present invention.

[0129] Preferably, the aluminum vapor deposition layer (b) continuously has an aluminum oxide layer (b1) and an aluminum layer (b2) in this order from the side in contact with the barrier layer (a), and in the elemental analysis in the depth direction of the aluminum oxide layer (b1), the maximum value of the molar ratio of oxygen element to aluminum element (O / Al) MAX measured by a scanning X-ray photoelectron spectroscopy apparatus is 0.5 or more and 2.0 or less, and in the depth direction analysis of the aluminum layer (b2), the minimum value of the molar ratio of oxygen element to aluminum element (O / Al) MIN measured by a scanning X-ray photoelectron spectroscopy apparatus is less than 0.5. The aluminum vapor deposition layer (b) has an aluminum oxide layer (b3) that includes the surface (s) opposite to the surface in contact with the barrier layer (a), and in the elemental analysis of the surface (s), the molar ratio of oxygen element to aluminum element (O / Al) S measured by a scanning X-ray photoelectron spectroscopy apparatus is more preferably 0.5 or more and 2.0 or less. The specific form and suitable form of the aluminum oxide layer (b1), the aluminum layer (b2), and the aluminum oxide layer (b3) are the same as the specific form and suitable form of the aluminum oxide layer (B1), the aluminum layer (B2), and the aluminum oxide layer (B3) in the aluminum vapor deposition layer (B) of the vapor deposition film of the present invention.

[0130] The multi-layer structure of the present invention may include two vapor deposition films of the present invention. The multi-layer structure of the present invention may include three or more vapor deposition films of the present invention. When the multi-layer structure of the present invention includes two or more vapor deposition films of the present invention, these vapor deposition films may be the same or different.

[0131] (Polyamide layer (F))

[0132] The multi-layer structure of the present invention may further include a polyamide layer (F), and the polyamide layer (F) is directly laminated or laminated via other layers on the vapor deposition film. By providing the multi-layer structure with the polyamide layer (F), the gas barrier property and the like can be further improved.

[0133] The vapor deposition film and the polyamide layer (F) may be directly laminated or laminated via other layers. Examples of the other layers include an adhesive layer, a polyolefin layer (E), and the like. Multiple layers may be present between multiple vapor deposition films.

[0134] The polyamide layer (F) is preferably at least one of the outermost layers in the multi-layer structure. In the multi-layer structure of the present invention, when formed in a bag shape, the outermost layer may be the polyamide layer (F). In one embodiment of the multi-layer structure of the present invention, one outermost layer may be a polyolefin layer (E) and the other outermost layer may be a polyamide layer (F).

[0135] The polyamide layer (F) generally contains polyamide as the main component. Polyamide refers to a resin containing amide bonds. Polyamide is obtained, for example, by ring-opening polymerization of lactams with 3 or more membered rings, polycondensation of polymerizable ω-amino acids, polycondensation of dibasic acids and diamines, etc. Examples of polyamide include polydecamide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecamide (nylon 11), polylaurolactam (nylon 12), polyhexamethylene adipamide (nylon 26), polyhexamethylene succinamide (nylon 46), polyhexamethylene adipamide (nylon 66), polydecamethylene adipamide (nylon 610), polydodecamethylene adipamide (nylon 612), polyhexamethylene octanediamide (nylon 86), polyhexamethylene sebacamide (nylon 108), caprolactam / laurolactam copolymer (nylon 6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon 6 / 9), caprolactam / hexamethylenediammonium adipate copolymer (nylon 6 / 66), laurolactam / hexamethylenediammonium adipate copolymer (nylon 12 / 66), hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon 66 / 610), ethylenediammonium adipate / hexamethylenediammonium adipate copolymer (nylon 26 / 66), caprolactam / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon 6 / 66 / 610), poly(m-phenylene adipamide) (nylon 6I), poly(p-phenylene adipamide) (nylon 6T), m-phenylene adipamide / p-phenylene adipamide copolymer (nylon 6I / 6T), etc.

[0136] As the content of polyamide in the polyamide layer (F), it is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, still more preferably 97% by mass or more and 100% by mass or less. In the polyamide layer (F), as components other than polyamide, it may contain antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, other resins other than polyamide, etc.

[0137] The polyamide layer (F) may be an unstretched layer or a stretched layer.

[0138] As the lower limit of the average thickness of the polyamide layer (F), it is preferably 1 μm, more preferably 3 μm, further preferably 5 μm, and still more preferably 10 μm. By making the average thickness of the polyamide layer (F) above the above lower limit, gas barrier properties, flex resistance, storage properties, etc. can be improved. As the upper limit of the average thickness of the polyamide layer (F), it is preferably 100 μm, more preferably 50 μm, and may be 30 μm. By making the average thickness of the polyamide layer (F) below the above upper limit, thinning of the multilayer structure can be achieved, etc.

[0139] The polyamide layer (F) may consist of a single layer or multiple layers.

[0140] (Other layers)

[0141] The multi-layer structure of the present invention may have other layers in addition to the above-mentioned vapor deposition film, polyolefin layer (E), and polyamide layer (F). Examples of other layers include an adhesive layer, other thermoplastic resin layers, a paper layer, a metal foil layer, etc.

[0142] When the multi-layer structure of the present invention has an adhesive layer, as the average thickness of the adhesive layer, for example, it is preferably 0.1 μm or more and 10 μm or less, more preferably 0.3 μm or more and 5 μm or less, and still more preferably 0.5 μm or more and 3 μm or less. By setting the average thickness of the adhesive layer within the above range, sufficient adhesiveness can be exhibited and the weight reduction of the multi-layer structure can be achieved, etc.

[0143] (Layer structure, etc.)

[0144] Examples of the layer structure of the multi-layer structure of the present invention include, for example:

[0145] (1) Vapor deposition film / / E,

[0146] (2) Vapor deposition film / / F / E,

[0147] (3) E / / Vapor deposition film / / E,

[0148] (4) E / / Vapor deposition film / / E / / E

[0149] (5) F / / Vapor deposition film / / E,

[0150] (6) E / / Vapor deposition film / / F / / E,

[0151] (7) F / / Vapor deposition film / / F / / E,

[0152] (8) E / / Vapor deposition film / / Vapor deposition film / / E,

[0153] (9) F / / Vapor deposition film / / Vapor deposition film / / E

[0154] (10) Vapor deposition film / / Vapor deposition film / / Vapor deposition film / / E

[0155] (11) F / Vapor deposition film / / Vapor deposition film / / Vapor deposition film / / E, etc.

[0156] It should be noted that E is a polyolefin layer and F is a polyamide layer. In the layer structures exemplified above, a layer structure in which other layers are arranged at any position is also an example of the multilayer structure of the present invention. The layer structure of the vapor deposition film in the layer structures exemplified above is as exemplified above. In addition, the orientation of the vapor deposition film is not particularly limited. For example, when the layer structure of the multilayer structure of the above (1), "vapor deposition film / / E", has a vapor deposition film with a layer structure of "A / B", it can be a layer structure of "A / B / / E" or a layer structure of "B / A / / E".

[0157] In the multilayer structure of the present invention, the thickness ratio of the barrier layer (A) to the total thickness of the multilayer structure (the average thickness of the barrier layer (A) to the average thickness of the entire multilayer structure) can be, for example, 10% or less, and is sometimes preferably 5% or less, more preferably 4% or less, 3% or less, or 2% or less. By making the thickness ratio of the barrier layer (A) below the above upper limit, there are advantages such as improved recyclability. For example, when recycled and melt-molded, the compatibility is excellent, and recycled products with excellent appearance can be molded. As the lower limit of the thickness ratio of the barrier layer (A), it is sometimes preferably 0.1%, more preferably 0.2%, 0.5%, or 1%. By making the thickness ratio of the barrier layer (A) above the above lower limit, the gas barrier property and the like can be improved.

[0158] As the lower limit of the average thickness of the multilayer structure of the present invention (the average thickness of the entire multilayer structure), it is preferably 10 μm, and can be 20 μm, 30 μm, or 50 μm. By making the average thickness of the multilayer structure above the above lower limit, the gas barrier property, bending resistance, storage property, etc. can be further improved. As the upper limit of the average thickness of the multilayer structure, it is preferably 1,000 μm, and can be 500 μm, 300 μm, 200 μm, or 100 μm. By making the average thickness of the multilayer structure below the above upper limit, weight reduction can be achieved, and moldability and the like can be improved.

[0159] The multilayer structure of the present invention can also be pulverized for reuse and used in the form of a melt molding material. The multilayer structure can be used in combination with other melt molding materials (other recycled resins, unused resins, etc.). The multilayer structure can be entirely reused in the form of a melt molding material, or the multilayer structure can be separated and only a part of it can be reused in the form of a melt molding material.

[0160] The method for manufacturing the multilayer structure of the present invention is not particularly limited. For example, a multilayer structure can be obtained by laminating a film of a polyolefin layer (E), a film of a polyamide layer (F), other vapor-deposited films, etc. on the vapor-deposited film by using known means such as dry lamination. In addition, a multilayer structure can also be obtained by laminating a polyolefin layer (E), a polyamide layer (F), etc. on the vapor-deposited film by using, for example, melt extrusion.

[0161] As uses of the multilayer structure of the present invention, various packaging materials such as food packaging, chemical packaging, industrial drug packaging, pesticide packaging, etc., vacuum insulation bags, etc. can be cited.

[0162] <Packaging material>

[0163] The packaging material of the present invention contains the vapor-deposited film of the present invention or the multilayer structure of the present invention. This packaging material is used for packaging purposes and its shape is not limited. This packaging material can be in a sheet form or can be formed into a specified shape such as a bag shape. From the viewpoints of heat sealability, etc., as the heat-sealing layer, the polyolefin layer (D) or the polyolefin layer (E) is preferably located on the outermost layer. In addition, from the viewpoints of heat sealability, etc., the polyolefin layer (D) or the polyolefin layer (E) located on the outermost layer is preferably unstretched. In the case of a packaging material formed into a shape having an inner side and an outer side such as a bag shape, the polyolefin layer (D) or the polyolefin layer (E) is preferably located at least on the innermost layer. From the viewpoint of further suppressing the decrease in gas barrier properties after storage of the packaging material, the aluminum vapor-deposited layer (B) is preferably arranged on the outer side compared with the barrier layer (A). Regarding the layer constitution specifically preferred as the packaging material, the outer layer side (E) / / (B) / (A) / (C) / (D) / / (E) inner layer side, etc. can be cited. In particular, if (A) / (C) / (D) are stretched and (E) is unstretched, there is a tendency to be able to balance the mechanical strength and heat seal of the packaging material, so it is preferred. In addition, if the total thickness of (D) / / (E) of the inner layer is 55 μm or more, even in the case of specific contents (contents with a water activity of 0.9 or more, a salt content of 0.5 g / g or more, or contents containing oil), the decrease in gas barrier properties after storage can be suppressed.

[0164] The packaging material of the present invention is used for packaging, for example, foods, beverages, chemical drugs, medical devices, machine parts, clothing, etc. In particular, this packaging material is preferably used for applications that require gas barrier properties against oxygen and applications where the inside of the packaging material is replaced with various functional gases. Since this packaging material has the vapor-deposited film of the present invention, the decrease in gas barrier properties after bending treatment and after storage is suppressed, and high gas barrier properties can be maintained for a long time. In addition, in the packaging material of the present invention, the aluminum vapor-deposited layer (B) is not easily peeled off from the barrier layer (A), so the degradation of the appearance after storage is also suppressed.

[0165] The packaging material is formed into various forms according to its use, such as a vertical bag filling and sealing bag, a soft pouch with a nozzle, a laminated tube container, a lid material for a container, a vacuum packaging bag, etc.

[0166] The vertical bag filling and sealing bag is used for packaging foods, beverages, etc. in the form of, for example, liquids, viscous substances, powders, solid dispersions, or combinations thereof. The vertical bag filling and sealing bag is formed by heat-sealing a vapor deposition film or a multilayer structure. In the case of heat-sealing, generally, a heat-sealable layer (such as polyolefin layer (D) or polyolefin layer (E)) needs to be provided as the layer that becomes the inner side of the vertical bag filling and sealing bag or both the layer that becomes the inner side and the layer that becomes the outer side of the vertical bag filling and sealing bag in the vapor deposition film or multilayer structure. When the heat-sealable layer exists only on the inner side of the vertical bag filling and sealing bag, the bag body is usually sealed by butt joint. When the heat-sealable layer exists on both the inner and outer sides of the vertical bag filling and sealing bag, the bag body is usually sealed by sealing joint.

[0167] The soft pouch with a nozzle is used for packaging liquid substances, such as liquid beverages like soft drinks, jelly drinks, yogurt, jam, seasonings, functional water, liquid foods, etc. The laminated tube container is used for packaging, for example, cosmetics, chemicals, pharmaceuticals, foods, toothpaste, etc. The lid material for a container is the lid material for a container to be filled with foods such as processed meat products, processed vegetable products, processed fishery products, fruits, etc.

[0168] <Vacuum packaging bag>

[0169] The vacuum packaging bag of the present invention includes a packaging bag formed of the packaging material of the present invention, and the inside of the packaging bag is decompressed. Examples of the uses for which such a vacuum bag is suitable include the preservation of foods, beverages, etc. and the outer packaging material of a vacuum insulator, etc. in a vacuum state. Since this vacuum packaging bag includes the vapor deposition film of the present invention, a decrease in gas barrier properties after bending and storage is suppressed, and a high vacuum state can be maintained for a long time. The multilayer structure preferably suitable for the vacuum packaging bag is a structure including a plurality of vapor deposition films. In addition, a structure including a polyamide layer (F) in a housing that requires high mechanical strength is preferred. Examples of the layer structure of the multilayer structure preferably suitable for the vacuum packaging bag include outer side (F) / / (A) / (B) / / (A) / (B) / / (E) inner side, outer side (F) / / (A) / (B) / / (B) / (A) / / (E) inner side, etc. More preferably, one of the barrier layers (A) is EVOH and the other is PET.

[0170] <Vacuum insulator>

[0171] The vacuum insulator of the present invention includes the vacuum packaging bag of the present invention and a core material disposed inside the vacuum packaging bag. In the vacuum insulator, the vacuum packaging bag is also referred to as an outer packaging material. The vacuum insulator is used for applications that require cold insulation and heat insulation. Examples of the core material include glass fiber and polyurethane foam. In the vacuum insulator, the core material is sealed in a vacuum state inside the vacuum packaging bag (outer packaging material). The vacuum packaging bag (outer packaging material) is formed by, for example, heat-sealing a vapor deposition film or a multilayer structure.

[0172] In the vacuum insulator of the present invention, since the vacuum packaging bag (outer packaging material) has the vapor deposition film, a decrease in gas barrier properties after bending treatment and storage is suppressed, and a high heat insulation effect can be maintained for a long time. The vacuum insulator can be used as a heat insulating material for household appliances such as refrigerators, hot water equipment, and rice cookers; a heat insulating material for housing such as wall parts, ceiling parts, roof interiors, and floor parts; a roof material; a heat insulating panel for vending machines, etc.

[0173] Examples

[0174] Hereinafter, examples are given to explain the present invention in detail, but the present invention is not limited to these examples.

[0175] It should be noted that hereinafter, the aluminum vapor deposition layer may sometimes be abbreviated as "Al vapor deposition layer", the polyolefin as "PO", and the polyamide as "PA".

[0176] <Material 1 used>

[0177] (Barrier layer (A))

[0178] · EVOH-1: EVOH, ethylene unit content is 32 mol%, saponification degree is 99.9 mol%, MFR (190 °C, 2.16 kg load) is 1.6 g / 10 minutes

[0179] · OPET: "Lumirror (registered trademark) P60" (manufactured by Toray Industries, Inc., biaxially stretched PET film, average thickness is 12 μm)

[0180] <Evaluation method 1>

[0181] (1) Molar ratio of oxygen element to aluminum element (O / Al) in the aluminum vapor deposition layer (B)

[0182] Regarding the aluminum vapor deposition layer (B) of the vapor deposition film obtained in the examples and comparative examples, using the scanning X-ray photoelectron spectroscopy apparatus "PHI Quntera SXM" manufactured by ULVAC-PHI, while sputtering along the thickness (depth) direction using argon gas, the molar ratio of oxygen element to aluminum element (O / Al) was measured. It should be noted that the X-ray source was AlKα (1486.6 eV), and the X-ray beam diameter was (25 W, 15 kV), and the measurement was carried out under the conditions of a measurement range of 300 μm in width × 300 μm in length, a signal reception angle of 45°, and a pressure of 1×10 -6 Pa.

[0183] The molar ratio of oxygen element to aluminum element at the measurement point where the molar ratio of oxygen element observed on the barrier layer (A) side (i.e., observed in the alumina layer (B1)) reaches the maximum value was set as (O / Al) MAX , and the molar ratio of oxygen element to aluminum element at the measurement point where the molar ratio of oxygen element becomes the minimum value (i.e., the aluminum layer (B2)) was set as (O / Al) MIN . In addition, the molar ratio of oxygen element to aluminum element (O / Al) of the surface (S) on the opposite side of the surface of the aluminum vapor deposition layer (B) in contact with the barrier layer (A) was also measured. S .

[0184] (2) Oxygen transmission rate (OTR)

[0185] A part was cut from the vapor deposition films obtained through the examples and comparative examples, and using the oxygen transmission rate measurement device OX-TRAN2 / 21 type (detection limit: 0.01 mL / (m 2 ·day·atm)) manufactured by MOCON INC., under the conditions of 20 °C and 65% RH, the OTR was measured according to the method described in ISO14663-2 Annex C (1999), and the evaluation was carried out according to the following criteria.

[0186] (Judgment criteria)

[0187] A: Less than 0.01 mL / (m 2 ·day·atm) (below the detection limit)

[0188] B: 0.01 mL / (m 2 ·day·atm) or more and less than 0.05 mL / (m 2 ·day·atm)

[0189] C: 0.05 mL / (m 2 ·day·atm) or more and less than 0.10 mL / (m 2 ·day·atm)

[0190] D: 0.10 mL / (m 2 ·day·atm) or more and less than 1.0 mL / (m 2 ·day·atm)

[0191] E: 1.0 mL / (m 2 ·day·atm) or more

[0192] (3) Difference in OTR before and after the bending test

[0193] Cut out a 21 cm × 30 cm sample from the vapor deposition film obtained through the examples and comparative examples. Use a rubbing tester (Gelbo Flex Tester) (BE - 1005) manufactured by TESTERSANGYO Co., Ltd. to conduct a rubbing test (bending test) in accordance with ASTM F 392. Specifically, form the cut vapor deposition film into a cylindrical shape with a diameter of 3.5 inches under an atmosphere of 23°C and 50% RH, fix both ends to the rubbing tester, and perform the following repeated reciprocating motion 3 times: Apply a twist with an angle of 440 degrees for the initial interval of 7 inches, the interval at maximum bending of 1 inch, and the first 3.5 inches of the stroke, and then perform a linear horizontal motion for the subsequent 2.5 inches. After the bending test, cut out a part of the bent portion of the vapor deposition film after the bending test, and use an oxygen transmission rate measuring device OX - TRAN2 / 21 type (detection limit: 0.01 mL / (m 2 ·day·atm)) manufactured by MOCON INC. to measure the OTR under the conditions of 20°C and 65% RH in accordance with the method described in ISO14663 - 2 Annex C (1999). Calculate the difference in OTR before and after the bending test (OTR after the test - OTR before the test), and evaluate the difference in OTR according to the following criteria. If the judgment is A - D, it is judged that the bending resistance is good.

[0194] (Judgment criteria)

[0195] A: Less than 0.05 mL / (m 2 ·day·atm)

[0196] B: 0.05 mL / (m 2 ·day·atm) or more and less than 0.10 mL / (m 2 ·day·atm 2 ·day·atm)

[0197] C: 0.10 mL / (m 2 ·day·atm) or more and less than 0.15 mL / (m 2 ·day·atm)

[0198] D: 0.15 mL / (m2 ·day·atm) or more and less than 0.20 mL / (m 2 ·day·atm)

[0199] E: 0.20 mL / (m 2 ·day·atm) or more

[0200] (4) Difference in OTR before and after the storage test

[0201] Using samples cut from a part of the vapor deposition film obtained through the examples and comparative examples, a storage test was carried out for 20 days in an atmosphere of 20 °C and 65% RH. For the samples after the storage test, an oxygen transmission rate measuring device OX-TRAN 2 / 21 type manufactured by MOCON INC. (detection limit is 0.01 mL / (m 2 ·day·atm)) was used. Under the conditions of 20 °C and 65% RH, the oxygen permeability was measured according to the method described in ISO 14663-2 Annex C (1999). Calculate the difference in OTR before and after the storage test (OTR after the test - OTR before the test), and evaluate according to the following criteria. If it is judged as A to D, it is judged that the storage property is good.

[0202] (Judgment criteria)

[0203] A: Less than 0.05 mL / (m 2 ·day·atm)

[0204] B: 0.05 mL / (m 2 ·day·atm) or more and less than 0.10 mL / (m 2 ·day·atm)

[0205] C: 0.10 mL / (m 2 ·day·atm) or more and less than 0.15 mL / (m 2 ·day·atm)

[0206] D: 0.15 mL / (m 2 ·day·atm) or more and less than 0.20 mL / (m 2 ·day·atm)

[0207] E: 0.20 mL / (m 2 ·day·atm) or more

[0208] [Example 1]

[0209] Using a single-screw extruder, EVOH-1 was melted at 240 °C. While extruding from the die onto the casting roll, air was blown at a wind speed of 30 m / s using an air knife to obtain an unstretched film with an average thickness of 170 μm. The obtained unstretched film was brought into contact with warm water at 80 °C for 10 seconds, and using a tenter-type simultaneous biaxial stretching device, it was stretched 3.2 times longitudinally and 3.0 times transversely at 90 °C, and further heat-treated for 5 seconds in a tenter set to 170 °C to obtain an EVOH biaxially stretched film (barrier layer (A)) with an average thickness of 12 μm and a total width of 3.6 m. While winding the obtained EVOH biaxially stretched film, it was cut into a width of 80 cm centered on the central position of the total width of the film to obtain an EVOH biaxially stretched film 4000 m long.

[0210] Regarding the obtained EVOH biaxially stretched film (evaporation substrate), using a take-up type vacuum evaporation device "EWA-105" manufactured by Nippon Vacuum Technology Co., Ltd. having a transfer chamber and an evaporation chamber, an aluminum layer (B) was formed by the following method. In "EWA-105", there is an unwinder and a winder on the transfer chamber side, and in the evaporation chamber, there is a crucible for heating aluminum and a cooling tank for cooling the film while transporting it, and the film is transported along the cooling tank. The cooling tank was cooled to -30 °C, and the obtained EVOH biaxially stretched film was transported at a transport speed of 150 m / min. Furthermore, a nozzle for directly blowing oxygen onto the EVOH biaxially stretched film before evaporation was installed in the evaporation chamber (nozzle gap: 2 mm, nozzle width: 21 cm, film-nozzle distance: 2 cm, angle relative to the film: 30 degrees), and while blowing oxygen at 80 mL / min, vacuum evaporation of aluminum was carried out to produce an evaporated film having an aluminum evaporation layer (B) with an average thickness of 40 nm formed on the EVOH biaxially stretched film. It should be noted that the pressure in the evaporation chamber was 5×10 -4 Pa to 9×10 -4 Pa. The average thickness of the aluminum evaporation layer (B) was adjusted by appropriately controlling the voltage applied to the crucible.

[0211] Regarding the obtained evaporated film, each evaluation was carried out according to the methods described in (1) to (4) of the above evaluation method 1. The results are shown in Table 1.

[0212] [Examples 2 - 7, Comparative Examples 1 - 3]

[0213] As described in Table 1, the oxygen supply amount blown during evaporation was changed, and except for this, an evaporated film was produced and evaluated by the same method as in Example 1. The results are shown in Table 1.

[0214] [Example 8]

[0215] During evaporation coating, change the conveyance speed of the EVOH biaxially stretched film to 75 m / min, and perform evaporation coating such that the average thickness of the aluminum evaporation coating layer becomes 80 nm. Except for this, use the same method as in Example 1 to produce an evaporation coating film and evaluate it. The results are shown in Table 1.

[0216] [Example 9]

[0217] Set the average thickness to 12 μm. Except for this, use the same method as in Example 1 to obtain an unstretched film. Use the obtained unstretched film directly as the evaporation coating substrate. Except for this, use the same method as in Example 1 to produce an evaporation coating film and evaluate it. The results are shown in Table 1.

[0218] [Example 10]

[0219] Use OPET to replace the EVOH biaxially stretched film. Except for this, use the same method as in Example 1 to produce an evaporation coating film and evaluate it. The results are shown in Table 1.

[0220] [Comparative Example 4]

[0221] Use OPET to replace the EVOH biaxially stretched film. Except for this, use the same method as in Comparative Example 3 to produce an evaporation coating film and evaluate it. The results are shown in Table 1.

[0222] [Comparative Example 5]

[0223] Install a nozzle in the evaporation coating chamber for directly spraying oxygen onto the evaporation coating layer of the EVOH biaxially stretched film after evaporation coating (the nozzle gap is 2 mm, the nozzle width is 21 cm, the film-nozzle distance is 2 cm, and the angle relative to the film is 90 degrees). Introduce oxygen from the nozzle for directly spraying oxygen onto the evaporation coating layer under the condition of 5000 mL / min or more, and introduce oxygen such that the pressure in the evaporation coating chamber becomes 1.0×10 -2 Pa to 5.0×10 -2 Pa. Except for this, use the same method as in Comparative Example 3 to produce an evaporation coating film and evaluate it. The results are shown in Table 1.

[0224] [Comparative Example 6]

[0225] Set the oxygen supply amount sprayed during evaporation coating to 5000 mL / min or more, and introduce oxygen such that the pressure in the evaporation coating chamber becomes 1.0×10 -2 Pa to 5.0×10 -2 Pa. Except for this, use the same method as in Example 1 to produce an evaporation coating film and evaluate it. The results are shown in Table 1.

[0226] [Comparative Example 7]

[0227] A crucible for heating aluminum in the evaporation chamber is provided, and a nozzle for blowing oxygen (nozzle gap: 2 mm, nozzle width: 21 cm) is provided so that oxygen can be blown between the transported EVOH biaxially stretched films. While blowing oxygen at 3000 - 5000 mL / minute, vacuum evaporation of aluminum oxide is carried out. In addition, using the same method as in Comparative Example 3, an evaporated film is produced and evaluated. The results are shown in Table 1.

[0228] [Table 1]

[0229]

[0230] <Materials Used 2>

[0231] (Barrier layer (A), barrier layer (a))

[0232] · EVOH-1: EVOH, ethylene unit content: 32 mol%, saponification degree: 99.9 mol%, MFR (190 °C, 2.16 kg load): 1.6 g / 10 minutes

[0233] · OPET: "Lumirror (registered trademark) P60" (manufactured by Toray Industries, Inc., biaxially stretched PET film, average thickness: 12 μm)

[0234] (PO layer (E))

[0235] · LLDPE: "UNILAX (registered trademark) LS760C" (manufactured by IDEMITSU UNITECH CORPORATION, LLDPE film, average thickness: 50 μm)

[0236] (PA layer (F))

[0237] · OPA: "EMBLEM (registered trademark) ONM15" biaxially stretched polyamide film, average thickness: 15 μm

[0238] <Evaluation Method 2>

[0239] (5) Thermal conductivity

[0240] After storing the vacuum insulators obtained from the examples and comparative examples at 23 °C and 50% RH for one week, using a thermal conductivity measuring device (manufactured by EIHON SEIKI CO., LTD., FOX314 type), one side of the vacuum insulator is set to 38 °C and the other side is set to 12 °C, and the thermal conductivity (mW / (m·k)) of the vacuum insulator is measured. Two evaluations are carried out, and the average value of the two evaluation results is set as the thermal conductivity before the test, and the evaluation is carried out according to the following criteria. If the evaluation result is A or B, it is judged that the heat insulation performance is good.

[0241] (Thermal conductivity before the test (judgment criteria))

[0242] A: Below 2.5 mW / m·K

[0243] B: Greater than 2.5 mW / m·K and below 2.8 mW / m·K

[0244] C: Greater than 2.8 mW / m·K

[0245] The vacuum heat insulators obtained through the examples and comparative examples were bent along a semi - arc with R = 115 mm. After the bent vacuum heat insulators were stored at 23°C and 50% RH for 1 week, they were pressed against a horizontal plate to restore them to a flat shape, and then the thermal conductivity of the vacuum heat insulators was measured in the same manner as above. Two evaluations were carried out, and the average value of the two evaluation results was set as the thermal conductivity after the bending test. The difference in thermal conductivity before and after the bending test (after the bending test - before the bending test) was calculated and evaluated according to the following criteria. If the evaluation result is A - C, it is judged that the bending resistance is good. That is, it can be considered that the reduction in gas barrier performance after the bending treatment is suppressed, and as a result, the reduction in thermal conductivity caused by bending is suppressed.

[0246] (Difference in thermal conductivity before and after the bending test (judgment criterion))

[0247] A: 0.1 mW / m·K or less

[0248] B: Greater than 0.1 mW / m·K and 0.3 mW / m·K or less

[0249] C: Greater than 0.3 mW / m·K and 0.5 mW / m·K or less

[0250] D: Greater than 0.5 mW / m·K

[0251] The vacuum heat insulators obtained through the examples and comparative examples were bent along a semi - arc with R = 115 mm. After the bent vacuum heat insulators were stored at 23°C and 50% RH for 1 week, they were stored in a dryer at 80°C for 60 days, then pressed against a horizontal plate to restore them to a flat shape, and then stored at 23°C and 50% RH for 1 week. The heat transfer coefficient was measured using a thermal conductivity measuring device in the same manner as above. Two evaluations were carried out, and the average value of the two evaluation results was set as the thermal conductivity after the storage test. The difference before and after the storage test (after the storage test - after the bending test) was calculated and evaluated according to the following criteria. If the evaluation result is A - C, it is judged that the storage property is good. That is, it can be considered that the reduction in gas barrier performance after storage is suppressed, and as a result, the reduction in thermal conductivity after storage is suppressed.

[0252] (Difference in thermal conductivity before and after the storage test (judgment criterion))

[0253] A: 7.0 mW / m·K or less

[0254] B: greater than 7.0 mW / m·K and less than or equal to 11.0 mW / m·K

[0255] C: greater than 11.0 mW / m·K and less than or equal to 15.0 mW / m·K

[0256] D: greater than 15.0 mW / m·K and less than or equal to 15.0 mW / m·K

[0257] [Example 11]

[0258] Prepare the vapor deposition film obtained in Example 8 as the first vapor deposition film.

[0259] Change the conveyance speed of PET during vapor deposition to 94 m / min, and perform vapor deposition so that the average thickness of the aluminum vapor deposition layer becomes 50 nm. Except for this, perform the same operations as in Example 10 to produce a second vapor deposition film (OPET / Al = 12 μm / 50 nm). For the obtained second vapor deposition film, measure the molar ratio (O / Al) of oxygen element to aluminum element in the aluminum vapor deposition layer according to the method described in (1) of the above Evaluation Method 1. The results are shown in Table 3. In addition, the results of the above molar ratio measurement of the vapor deposition film (the first vapor deposition film) obtained in Example 8 are also recorded again in Table 3. It should be noted that the aluminum vapor deposition layer in the vapor deposition film (the first vapor deposition film) of Example 8 is denoted as aluminum vapor deposition layer (B), and the aluminum vapor deposition layer of the second vapor deposition film is denoted as aluminum vapor deposition layer (b).

[0260] On the surface of the aluminum vapor deposition layer of the second vapor deposition film, on one side of OPA, and on one side of LLDPE, coat a two-component urethane-based adhesive (''TAKERAC (trademark) A-520'' and ''TAKENATE (trademark) A-50'' manufactured by Mitsui Chemicals, Inc.) so that the average thickness after drying becomes 1.0 μm, and dry it. Also use the first vapor deposition film to perform lamination in such a way as to present the structure of OPA / tie / PET / Al / tie / Al / EVOH-1 / tie / LLDPE (tie refers to the adhesive layer, and Al refers to the aluminum vapor deposition layer) to produce a multilayer structure.

[0261] Using the obtained multilayer structure, a vacuum heat insulator is fabricated. Specifically, the multilayer structure is cut into 20 cm × 40 cm, two cover materials are produced, and the two cover materials are overlapped such that the LLDPE layers face each other as the inner surfaces, and three sides are heat-sealed with a width of 10 mm to produce a packaging bag as a three-sided sealed bag. Glass fiber dried for 4 hours in an atmosphere of 160 °C, which is a low thermal conductivity core material, and a sachet filled with calcium oxide as an adsorbent are filled respectively from the opening parts of the obtained packaging bag, and using a vacuum heat insulation panel manufacturing device (manufactured by NPC Corporation, model KT-500RD), at a temperature of 20 °C, the packaging bag is sealed in a state where the internal pressure is 1.0 Pa to produce a vacuum heat insulator. Regarding the obtained vacuum heat insulator, the thermal conductivity is evaluated according to the method described in (5) of the above evaluation method 2. The results are shown in Table 3.

[0262] [Examples 12 and 13]

[0263] As described in Table 2, the oxygen supply amount blown during evaporation is changed, and in addition, using the same method as in Example 8, an evaporation film is produced and used as the first evaporation film. In addition, using the same method as in Example 11, evaporation films, multilayer structures, and vacuum heat insulators are produced and evaluated. The results are shown in Table 3.

[0264] [Example 14]

[0265] The average thickness is set to 12 μm, and in addition, using the same method as in Example 8, an unstretched film is obtained. The obtained unstretched film is directly used as the evaporation substrate, and in addition, using the same method as in Example 8, an evaporation film is produced and the obtained evaporation film is used as the first evaporation film. In addition, using the same method as in Example 11, evaporation films, multilayer structures, and vacuum heat insulators are produced and evaluated. The results are shown in Table 3.

[0266] [Example 15]

[0267] The evaporation film obtained in Example 1 is used as the first evaporation film, and in addition, using the same method as in Example 11, evaporation films, multilayer structures, and vacuum heat insulators are produced and evaluated. The results are shown in Table 3.

[0268] [Comparative Example 8]

[0269] The evaporation film obtained in Comparative Example 1 is used as the first evaporation film, and furthermore, when producing the second evaporation film, oxygen is not blown, and in addition, using the same method as in Example 11, evaporation films, multilayer structures, and vacuum heat insulators are produced and evaluated. The results are shown in Table 3.

[0270] [Comparative Example 9]

[0271] Use the vapor-deposited film obtained in Comparative Example 2 as the first vapor-deposited film. Except for this, use the same method as in Comparative Example 8 to produce a vapor-deposited film, a multilayer structure, and a vacuum heat insulator, and evaluate them. The results are shown in Table 3.

[0272] [Comparative Example 10]

[0273] Use the vapor-deposited film obtained in Comparative Example 3 as the first vapor-deposited film. Except for this, use the same method as in Comparative Example 8 to produce a vapor-deposited film, a multilayer structure, and a vacuum heat insulator, and evaluate them. The results are shown in Table 3.

[0274] [Table 2]

[0275]

[0276] [Table 3]

[0277]

[0278] <Material 3 used>

[0279] (Barrier layer (A))

[0280] · EVOH-2: EVOH, ethylene unit content is 48 mol%, saponification degree is 99.9 mol%, MFR (190 °C, 2.16 kg load) is 6.4 g / 10 min

[0281] · EVOH-3: EVOH, ethylene unit content is 32 mol%, saponification degree is 99.9 mol%, MFR (190 °C, 2.16 kg load) is 1.6 g / 10 min

[0282] · OPET: "Lumirror (registered trademark) P60" (manufactured by Toray Industries, Inc., biaxially oriented PET film, average thickness is 12 μm)

[0283] (Adhesive resin layer (C))

[0284] · Ad: "ADMER (registered trademark) NF528" (manufactured by Mitsui Chemicals, Inc., maleic anhydride-modified polyethylene)

[0285] (PO layer (D))

[0286] · PP: "Novatec (registered trademark) FL203D" (manufactured by Japan Polypropylene Corporation, polypropylene)

[0287] (PO layer (E))

[0288] · OPP: "FOR" (manufactured by Futamura Chemical Co., Ltd., biaxially oriented polypropylene film, average thickness is 20 μm)

[0289] · CPP30: "GLC" (Mitsui Chemicals Tohcello, unstretched polypropylene film, average thickness 30 μm)

[0290] · CPP50: "GLC" (Mitsui Chemicals Tohcello, unstretched polypropylene film, average thickness 50 μm)

[0291] <Evaluation Method 3>

[0292] (6) OTR before storage test

[0293] Cut out 11 cm × 11 cm from the multilayer structures obtained in the examples and comparative examples. For the cut measurement samples, after standing for 1 week at 20 °C and 65% RH, use an oxygen transmission rate measuring device OX-TRAN2 / 21 type manufactured by MOCON INC. (detection limit 0.01 mL / (m 2 · day·atm)), under the conditions of 20 °C and 65% RH, measure the oxygen permeability according to the method described in ISO14663-2 Annex C (1999), and evaluate according to the following criteria.

[0294] (Judgment criteria)

[0295] A: Less than 0.01 mL / (m 2 · day·atm)

[0296] B: 0.01 mL / (m 2 · day·atm) or more and less than 0.05 mL / (m 2 · day·atm)

[0297] C: 0.05 mL / (m 2 · day·atm) or more and less than 0.10 mL / (m 2 · day·atm)

[0298] D: 0.10 mL / (m 2 · day·atm) or more and less than 0.2 mL / (m 2 · day·atm)

[0299] E: 0.2 mL / (m 2 · day·atm) or more

[0300] (7) OTR and appearance after storage test

[0301] A storage test was conducted on the flexible pouches filled with ketchup obtained from the examples and comparative examples by storing them in a thermo-hygrostat set at 43°C and 50% RH for 150 days. After the storage test, the upper part of the flexible pouch was cut off, the ketchup was taken out, the attached matter was washed with pure water, and after wiping off the attached pure water with a paper towel, a square of 11 cm × 11 cm (excluding the sealed part) was cut from the central part of the flexible pouch. For the cut measurement samples, they were conditioned at 20°C and 65% RH for 1 week, and using the oxygen transmission rate measuring device OX-TRAN2 / 21 type manufactured by MOCON INC. (the detection limit is 0.01 mL / (m 2 ·day·atm)), under the conditions of 20°C and 65% RH, according to the method described in ISO14663-2 Annex C (1999), the oxygen permeability was measured, and the evaluation was carried out according to the following criteria.

[0302] (OTR Judgment Criteria)

[0303] A: Less than 0.1 mL / (m 2 ·day·atm)

[0304] B: 0.1 mL / (m 2 ·day·atm) or more and less than 0.5 mL / (m 2 ·day·atm)

[0305] C: 0.5 mL / (m 2 ·day·atm) or more and less than 1.0 mL / (m 2 ·day·atm)

[0306] D: 1.0 mL / (m 2 ·day·atm) or more and less than 2.0 mL / (m 2 ·day·atm)

[0307] E: 2.0 mL / (m 2 ·day·atm) or more

[0308] In addition, the appearance after the storage test was evaluated according to the following criteria.

[0309] (Appearance Judgment Criteria)

[0310] A: The same as before the storage test

[0311] B: Whitening with a maximum length of 0.1 mm or more and less than 5 mm was observed

[0312] C: Whitening with a maximum length of 5 mm or more and 25 or more and less than 10 mm was observed

[0313] D: Whitening with a maximum length of 10 or more and less than 20 mm was observed

[0314] E: Whitening with a maximum length of 20 mm or more was observed.

[0315] [Example 16]

[0316] Using EVOH-2 as the material for the barrier layer (A), Ad as the material for the adhesive resin layer (C), and PP as the material for the PO layer (D), a non-stretched multilayer film (EVOH-2 / Ad / PP = 10 μm / 10 μm / 180 μm) was produced by a three-layer co-extrusion casting method using three types of equipment. The film was extruded from the die onto the casting roll, and at the same time, air was blown using an air knife at a wind speed of 30 m / s under the following conditions.

[0317] (Multilayer film production conditions)

[0318] Equipment: Three-layer casting film co-extrusion molding machine

[0319] Barrier layer (A): EVOH-2

[0320] Extruder: Single-screw extruder (Toyo Seiki Co., Ltd. test machine ME type CO-EXT)

[0321] Screw: Diameter L / D 20, full-thread screw

[0322] Extrusion temperature: Feeding section / Compression section / Metering section / Die = 175 / 200 / 220 / 220 °C

[0323] Adhesive resin layer (C): Ad

[0324] Extruder: Single-screw extruder (TECHNOVEL Co., Ltd., SZW20GT-20MG)

[0325] Screw: Diameter L / D 20, full-thread screw

[0326] Extrusion temperature: Feeding section / Compression section / Metering section / Die = 175 / 200 / 220 / 220 °C

[0327] PO layer (D): PP

[0328] Extruder: Single-screw extruder (Plastic Engineering Institute Co., Ltd., GT-32-A)

[0329] Screw: Diameter L / D 28, full-thread screw

[0330] Extrusion temperature: Feeding section / Compression section / Metering section / Die = 175 / 200 / 220 / 220 °C

[0331] Mold: Three 3-layer hanger molds with a width of 300 mm (manufactured by Plastic Engineering Research Institute Co., Ltd.)

[0332] Using a tenter-frame type simultaneous biaxial stretching device, the obtained unstretched multilayer film was stretched 3.2 times longitudinally and 3.0 times transversely at 160 °C to obtain a biaxially stretched multilayer film with EVOH-2 / Ad / PP = 1 μm / 1 μm / 18 μm.

[0333] Using the same method as in Example 1, vacuum evaporation of aluminum was performed on the barrier layer (A) of the obtained biaxially stretched multilayer film to produce a vapor-deposited film (aluminum vapor-deposited layer / EVOH-2 / Ad / PP = 40 nm / 1 μm / 1 μm / 18 μm) having an aluminum vapor-deposited layer with an average thickness of 40 nm formed on the barrier layer (A). For the obtained vapor-deposited film, the molar ratio of oxygen element to aluminum element (O / Al) in the aluminum vapor-deposited layer (B) was measured according to the method described in (1) of the above Evaluation Method 1. The results are shown in Table 5.

[0334] On one side of OPP and one side of CPP50, a two-component urethane-based adhesive (''TAKERAC (trademark) A-520'' and ''TAKENATE (trademark)'' A-50'' manufactured by Mitsui Chemicals, Inc.) was coated so that the average thickness after drying became 2 μm, and it was dried to provide an adhesive layer. Thereafter, OPP (PO layer (E1)) having an adhesive layer was laminated on the aluminum vapor-deposited side of the vapor-deposited film produced above, and CPP50 (PO layer (C2)) having an adhesive layer was laminated on the PO layer (D) side, and lamination was performed while performing roll crimping at 70 °C. Thereafter, by curing at 40 °C for 4 days, a multilayer structure (OPP / tie / Al / EVOH-2 / Ad / PP / tie / CPP = 20 μm / 2 μm / 40 nm / 1 μm / 1 μm / 18 μm / 2 μm / 50 μm (tie refers to the adhesive layer, and Al refers to the aluminum vapor-deposited layer)) was obtained. For the obtained multilayer structure, the OTR before the storage test was evaluated according to the method described in (6) of the above Evaluation Method 3. The results are shown in Table 5.

[0335] The obtained multi-layer structure was cut to produce two pieces of covering material with dimensions of 15 cm in width and 20 cm in length. They were overlapped with the CPP layers facing each other as the inner surfaces, and three sides were heat-sealed with a width of 10 mm to produce a packaging bag as a three-sided sealed bag. 50 g of ketchup made by KAGOME Co., Ltd. was put in it. Using a vacuum packaging machine VAC-STAR 2500GSL made by Frimrk Gmbh, the part with a length of 15 cm in the longitudinal direction (the remaining side that was not heat-sealed) was heat-sealed with a width of 10 mm to produce a flexible package bag with a size of 15 cm in width and 15 cm in length and vacuum-packed with 50 g of ketchup. For the obtained flexible package bag, according to the method described in (7) of the above evaluation method 3, the OTR and appearance after the storage test were evaluated. The results are shown in Table 5.

[0336] [Examples 17 - 22, Comparative Examples 11 - 13]

[0337] When producing the vapor deposition film in Example 16, the oxygen supply amount was changed as described in Table 4. Except for this, the biaxially stretched multi-layer film, vapor deposition film, multi-layer structure, and flexible package bag were produced using the same method and evaluated. The results are shown in Table 5.

[0338] [Example 23]

[0339] When producing the multi-layer structure, the PO layer (E2) (CPP50) was not laminated. Except for this, the biaxially stretched multi-layer film, vapor deposition film, multi-layer structure, and flexible package bag were produced using the same method as in Example 20 and evaluated. The results are shown in Table 5.

[0340] [Example 24]

[0341] When producing the multi-layer structure, the PO layer (E2) (CPP50) was not laminated. Except for this, the biaxially stretched multi-layer film, vapor deposition film, multi-layer structure, and flexible package bag were produced using the same method as in Example 17 and evaluated. The results are shown in Table 5.

[0342] [Example 25]

[0343] The conveying speed of the biaxially stretched multi-layer film during vapor deposition was changed to 75 m / min, and vapor deposition was carried out so that the average thickness of the aluminum vapor deposition layer became 80 nm. Except for this, the biaxially stretched multi-layer film, vapor deposition film, multi-layer structure, and flexible package bag were produced using the same method as in Example 23 and evaluated. The results are shown in Table 5.

[0344] [Example 26]

[0345] The conveyance speed of the biaxially stretched multilayer film during vapor deposition was changed to 75 m / min, and vapor deposition was performed such that the average thickness of the aluminum vapor-deposited layer became 80 nm. Except for this, a biaxially stretched multilayer film, a vapor-deposited film, a multilayer structure, and a flexible pouch were produced and evaluated using the same method as in Example 24. The results are shown in Table 5.

[0346] [Example 27]

[0347] When producing the multilayer structure, CPP30 was used as the PO layer (E2) instead of CPP50. Except for this, a biaxially stretched multilayer film, a vapor-deposited film, a multilayer structure, and a flexible pouch were produced and evaluated using the same method as in Example 16. The results are shown in Table 5.

[0348] [Example 28]

[0349] It was adjusted so that the average thickness of each layer of the unstretched multilayer film became EVOH-2 / Ad / PP = 30 μm / 30 μm / 108 μm for production. After heating the obtained unstretched multilayer film to 160 °C, it was stretched 6 times in the longitudinal direction (MD direction) using a roll stretching machine to produce a uniaxially stretched multilayer film (EVOH-2 / Ad / PP = 5 μm / 5 μm / 18 μm). The obtained uniaxial multilayer film was directly used as the vapor deposition substrate. Except for the above aspects, a vapor-deposited film, a multilayer structure, and a flexible pouch were produced and evaluated using the same method as in Example 27. The results are shown in Table 5.

[0350] [Example 29]

[0351] An unstretched multilayer film (EVOH-2 / Ad / PP = 5 μm / 5 μm / 18 μm) was produced such that the average thicknesses of the barrier layer (A), the adhesive resin layer (C), and the PO layer (D) became the average thicknesses described in Table 3. The obtained unstretched multilayer film was directly used as the vapor deposition substrate. Except for this, an unstretched multilayer film, a vapor-deposited film, a multilayer structure, and a flexible pouch were produced and evaluated using the same method as in Example 27. The results are shown in Table 5.

[0352] [Example 30]

[0353] EVOH-3 was used as the barrier layer (A). Except for this, an unstretched multilayer film, a vapor-deposited film, a multilayer structure, and a flexible pouch were produced and evaluated using the same method as in Example 29. The results are shown in Table 5.

[0354] [Example 31]

[0355] As the vapor deposition film, the vapor deposition film produced in Example 10 was used. Except for this, a multilayer structure and a flexible pouch were produced and evaluated by the same method as in Example 30. It should be noted that the CPP30 layer was laminated on the OPET side. The results are shown in Table 5.

[0356] [Comparative Example 14]

[0357] As the vapor deposition film, the vapor deposition film produced in Comparative Example 4 was used. Except for this, a multilayer structure and a flexible pouch were produced and evaluated by the same method as in Example 30. It should be noted that the CPP30 layer was laminated on the OPET side. The results are shown in Table 5.

[0358] [Table 4]

[0359]

[0360] [Table 5]

[0361]

[0362] As shown in Table 1, the vapor deposition films of Examples 1 to 10 have good bending resistance and storage properties. As shown in Tables 2 and 3, the vacuum heat insulators obtained from the multilayer structures of Examples 11 to 15 have good heat insulation performance, bending resistance and storage properties. As shown in Tables 4 and 5, the flexible pouches obtained from the multilayer structures of Examples 16 to 31 have good gas barrier properties before and after storage, and also have good appearance after storage. In addition, it was confirmed that when aluminum vapor deposition was performed, a small amount of oxygen was blown onto the vapor deposition substrate (barrier layer (A)), and the oxygen supply amount was adjusted, whereby the maximum value of the molar ratio of oxygen element to aluminum element in the aluminum oxide layer (B1) (O / Al) could be controlled. MAX . It should be noted that Examples 23 to 26 do not contain a CPP layer. Therefore, when heat-sealing the flexible pouch, the appearance of the flexible pouch deteriorates.

[0363] Explanation of reference numerals

[0364] 10 Vapor deposition film

[0365] A Barrier layer (A)

[0366] B Aluminum vapor deposition layer (B)

[0367] B1 Aluminum oxide layer (B1)

[0368] B2 Aluminum layer (B2)

[0369] B3 Aluminum oxide layer (B3)

[0370] S The opposite side of the surface of the aluminum vapor deposition layer (B) that contacts the barrier layer (A)

Claims

1. A vapor deposition film having a resinous barrier layer (A) and an aluminum vapor deposition layer (B), wherein the aluminum vapor deposition layer (B) is directly laminated on the barrier layer (A), and has an average thickness of 30 nm or more and 100 nm or less. The aluminum vapor deposition layer (B) successively and continuously has an aluminum oxide layer (B1) and an aluminum layer (B2) from the side in contact with the barrier layer (A). In the elemental analysis in the depth direction of the alumina layer (B1), the maximum value (O / Al) of the molar ratio of oxygen element to aluminum element measured using a scanning X-ray photoelectron spectroscopy analyzer MAX is 0.5 or more and 2.0 or less, In the depth direction analysis of the aluminum layer (B2), the minimum value (O / Al) of the molar ratio of oxygen element to aluminum element measured by a scanning X-ray photoelectron spectroscopy analyzer MIN is less than 0.

5.

2. The vapor deposition film according to claim 1, wherein, The aluminum vapor deposition layer (B) has an aluminum oxide layer (B3) which includes the surface (S) on the side opposite to the side in contact with the barrier layer (A). In the elemental analysis of the surface (S), the molar ratio of oxygen element to aluminum element (O / Al) measured using a scanning X-ray photoelectron spectroscopy analyzer S is 0.5 or more and 2.0 or less.

3. The vapor deposition film according to claim 1 or 2, wherein The barrier layer (A) contains at least one selected from ethylene alcohol-based polymers and polyester-based resins as the main component.

4. The vapor deposition film according to any one of claims 1 to 3, wherein, The barrier layer (A) is biaxially stretched.

5. The vapor deposition film according to any one of claims 1 to 4, wherein, The average thickness of the barrier layer (A) is 0.1 μm or more and 20 μm or less.

6. The vapor deposition film according to any one of claims 1 to 5, wherein, The average thickness of the aluminum vapor deposition layer (B) is 55 nm or more and 90 nm or less.

7. The vapor deposition film according to any one of claims 1 to 6, further having a polyolefin layer (D), wherein the polyolefin layer (D) is laminated on the surface of the barrier layer (A) opposite to the aluminum vapor deposition layer (B) via an adhesive resin layer (C).

8. The vapor deposition film according to claim 7, wherein, The barrier layer (A), the adhesive resin layer (C), and the polyolefin layer (D) are stretched at least along a uniaxial direction.

9. A multilayer structure comprising the vapor deposition film according to claim 7 or 8 and a polyolefin layer (E), wherein the polyolefin layer (E) is directly laminated or laminated via other layers on at least one surface of the vapor deposition film.

10. The multi-layer structure according to claim 9, wherein, The polyolefin layer (E) is directly laminated or laminated via other layers on both surfaces of the above-mentioned vapor deposition film, and each polyolefin layer (E) contains the same resin as the main component.

11. The multi-layer structure according to claim 9 or 10, wherein, The thickness ratio of the barrier layer (A) to the total thickness of the above-mentioned multilayer structure is 5% or less.

12. A multilayer structure comprising the vapor deposition film according to any one of claims 1 to 6 and a polyolefin layer (E), wherein the polyolefin layer (E) is directly laminated or laminated via other layers on the above-mentioned vapor deposition film.

13. The multilayer structure according to claim 12, further comprising another vapor deposition film, wherein the another vapor deposition film is directly laminated or laminated via other layers on the above-mentioned vapor deposition film. The another vapor deposition film has a resinous barrier layer (a) and an aluminum vapor deposition layer (b), wherein the aluminum vapor deposition layer (b) is directly laminated on the barrier layer (a), and has an average thickness of 30 nm or more and 100 nm or less.

14. The multilayer structure according to claim 13, wherein, The aluminum vapor deposition layer (b) successively and continuously has an aluminum oxide layer (b1) and an aluminum layer (b2) from the side in contact with the barrier layer (a). In the elemental analysis in the depth direction of the alumina layer (b1), the maximum value (O / Al) of the molar ratio of oxygen element to aluminum element measured by a scanning X-ray photoelectron spectroscopy analyzer MAX is 0.5 or more and 2.0 or less, In the depth direction analysis of the aluminum layer (b2), the minimum value of the molar ratio of oxygen element to aluminum element (O / Al) measured by a scanning X-ray photoelectron spectroscopy analyzer MIN is less than 0.

5.

15. The multilayer structure according to any one of claims 12 to 14, further comprising a polyamide layer (F), wherein the polyamide layer (F) is directly laminated or laminated via other layers on the above-mentioned vapor deposition film.

16. A packaging material comprising the vapor deposition film according to any one of claims 1 to 8 or the multilayer structure according to any one of claims 9 to 15.

17. A vacuum packaging bag comprising a packaging bag formed of the packaging material according to claim 16. The inside of the above-mentioned packaging bag is depressurized.

18. A vacuum insulator comprising: The vacuum packaging bag according to claim 17; and A core material disposed inside the above-mentioned vacuum packaging bag.

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