Vapor-deposited film, multilayer structure, and use of multilayer structure

Abstract

In a vapor-deposited film (X) in which a vapor-deposited layer (B) having a thickness of 30-200 nm and formed of silicon oxide or a metal oxide is directly formed on the surface of an ethylene-vinyl alcohol copolymer layer (A), when the surface of the vapor-deposited layer (B) on the ethylene-vinyl alcohol copolymer layer (A) side is defined as a surface (b1), the surface on the reverse side of the vapor-deposited layer (B) is defined as a surface (b2), and elemental analysis of the vapor-deposited layer (B) is performed in the depth direction by a scanning X-ray photoelectron spectroscopic analyzer from the surface (b2) to the surface (b1), the ratio [(O / M)b1 / (O / M)c] of the molar ratio (O / M)b1 of an oxygen element (O) to a silicon element or a metal element (M) in the surface (b1) to the molar ratio (O / M)c of the oxygen element (O) to the silicon element or the metal element (M) at a position equidistant from the surface (b1) and the surface (b2) is 1.1-1.7. Consequently, provided is a vapor-deposited film having excellent gas barrier properties, bending resistance, and radio wave transmitting properties.

Description

Deposited films, multilayer structures and applications of multilayer structures

[0001] The present invention relates to a vapor-deposited film containing an ethylene-vinyl alcohol copolymer layer and a vapor-deposited layer, and a multilayer structure containing the same.The present invention also relates to a packaging material containing the multilayer structure.The present invention further relates to a vacuum packaging bag formed from the packaging material and a vacuum insulator using the same.The present invention also relates to a package containing an item with an RFID tag attached inside the packaging material or inside a container surrounded by the vacuum insulator.

[0002] Insulation materials made of urethane foam (polyurethane foam) are used as insulation materials for refrigerators, insulation panels for homes, and the like. In recent years, vacuum insulators containing aluminum foil or an aluminum vapor-deposited layer have also been used as an alternative insulation material. Because vacuum insulators achieve insulation properties equivalent to those of insulation made of urethane foam with thinner and lighter insulation, their applications and demand are expanding as insulation materials used to insulate heat transfer devices such as heat pump-applied devices, heat storage devices, living spaces, vehicle interiors, and the like. However, because vacuum insulators use aluminum foil or an aluminum vapor-deposited film, they have poor radio wave permeability, making it difficult to apply RFID technology, an automatic identification technology that uses radio waves to read and write information on RFID tags (also called RF tags or IC tags) without contact.

[0003] One of the properties required for vacuum packaging bags for vacuum insulators is barrier property. For this reason, vacuum packaging bags with improved barrier property have been proposed. For example, Patent Document 1 describes a multilayer structure as a film used for vacuum packaging bags with improved gas barrier property, which has a vapor-deposited layer made of an inorganic oxide on at least one surface of a biaxially stretched polyvinyl alcohol film and a coating layer containing an organic polymer adjacent to the vapor-deposited layer.

[0004] International Publication No. 2016 / 159140

[0005] When vacuum packaging bags, vacuum insulators, etc. having a predetermined shape are produced from vapor-deposited films, they are usually completed through processing steps including folding, etc. Therefore, when vacuum packaging bags, vacuum insulators, etc. are produced using conventional vapor-deposited films, the gas barrier properties are sometimes reduced due to the physical stress applied during production, making it impossible to maintain the heat insulating performance for a long period of time.

[0006] An object of the present invention is to provide a vapor-deposited film having excellent gas barrier properties, flex resistance, and radio wave transmittance, a multilayer structure including the vapor-deposited film, a packaging material including the multilayer structure, a vacuum packaging bag and a vacuum insulator formed from the packaging material, a package comprising the packaging material and an article having an RFID tag attached thereto, and a package comprising the packaging material and an article having an RFID tag attached thereto and inside a container surrounded by the vacuum insulator.

[0007] As a result of extensive research into achieving the above-mentioned object, the present inventors have found that it is possible to obtain a vapor-deposited film with excellent gas barrier properties, flex resistance, and radio wave transmittance by (1) using an ethylene-vinyl alcohol copolymer layer as a substrate on which a vapor-deposited layer is formed, (2) forming a vapor-deposited layer made of silicon oxide or a metal oxide, and (3) blowing in an appropriate amount of oxygen gas when forming the vapor-deposited layer, thereby appropriately segregating oxygen element in the vapor-deposited layer, and have completed the present invention.

[0008] That is, the present invention is as follows: [1] A vapor-deposited film (X) comprising an ethylene-vinyl alcohol copolymer layer (A) and a vapor-deposited layer (B) made of silicon oxide or a metal oxide, wherein the vapor-deposited layer (B) having a thickness of 30 nm or more and 200 nm or less is formed directly on the surface of the ethylene-vinyl alcohol copolymer layer (A), wherein the surface of the vapor-deposited layer (B) facing the ethylene-vinyl alcohol copolymer layer (A) is designated as surface (b1) and the surface opposite to the vapor-deposited layer (B) is designated as surface (b2), and when elemental analysis of the vapor-deposited layer (B) is performed in the depth direction from surface (b2) to surface (b1) using a scanning X-ray photoelectron spectrometer, the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) in surface (b1) is ｂ１and the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) at positions equidistant from the surface (b1) and the surface (b2). ｃ The ratio [(O / M) ｂ１ / (O / M) ｃ [2] The vapor-deposited film (X) according to [1], in which the ethylene-vinyl alcohol copolymer layer (A) is stretched at least uniaxially. [3] The vapor-deposited film (X) according to [1] or [2], in which the ethylene-vinyl alcohol copolymer layer (A) has a thickness of 1 μm or more and 100 μm or less. [4] The vapor-deposited film (X) according to any one of [1] to [3], in which the vapor-deposited layer (B) consists of silicon oxide or aluminum oxide. [5] The vapor-deposited film (X) according to [4], in which the vapor-deposited layer (B) consists of silicon oxide. [6] The vapor-deposited film (X) according to [4], in which the molar ratio (O / M) ｂ１ [7] The vapor-deposited film (X) according to any one of [1] to [5], wherein the molar ratio (O / M) is 1.85 or more and 2.35 or less. ｃ

[0023] The vapor-deposited film (X) according to any one of [1] to [6], wherein the modulus of curvature (T) is 1.5 or more and 2.0 or less. [8] A multilayer structure comprising the vapor-deposited film (X) according to any one of [1] to [7] and a polyolefin layer (C) laminated together. [9] The multilayer structure according to [8], comprising a vapor-deposited film (Y) comprising a polyester layer (D) and a vapor-deposited layer (E) made of silicon oxide or a metal oxide, a vapor-deposited film (X), and a polyolefin layer (C) laminated together in this order.

[10] The multilayer structure according to [8], comprising a polyamide layer (F), a vapor-deposited film (X), and a polyolefin layer (C) laminated together in this order.

[11] The multilayer structure according to

[10] , comprising a polyamide layer (F), a vapor-deposited film (Y), a vapor-deposited film (X), and a polyolefin layer (C) laminated together in this order.

[12] A packaging material comprising the multilayer structure according to any one of [8] to

[11] .

[13] A package comprising an article with an RFID tag attached thereto, housed inside the packaging material according to

[12] .

[14] A vacuum packaging bag formed from the packaging material described in

[12] .

[15] A vacuum insulator having a core material disposed inside the vacuum packaging bag described in

[14] and having a reduced pressure inside.

[16] A package comprising a container surrounded by the vacuum insulator described in

[15] and containing an item with an RFID tag attached thereto.

[0009] The vapor-deposited film of the present invention has excellent gas barrier properties and flex resistance, and therefore can provide multilayer structures, vacuum packaging bags, and vacuum insulators that can maintain high barrier properties even when subjected to physical stress such as flexing. Furthermore, the vapor-deposited film of the present invention has excellent radio wave transmittance, and therefore RFID technology can be applied to packaging materials, vacuum packaging bags, vacuum insulators, and the like produced using the vapor-deposited film.

[0010] 1 is a graph plotting the molar ratios of silicon (Si), oxygen (O), and carbon (C) (total 100 mol%) against sputtering time when the vapor deposition layer (B) formed in Example 2 was analyzed with a scanning X-ray photoelectron spectrometer. FIG. 2 is a graph plotting the molar ratio (O / Si) calculated from FIG. 1 against sputtering time. FIG. 3 is a graph plotting the molar ratios of silicon (Si), oxygen (O), and carbon (C) (total 100 mol%) against sputtering time when the vapor deposition layer (B) formed in Comparative Example 5 was analyzed with a scanning X-ray photoelectron spectrometer. FIG. 4 is a graph plotting the molar ratio (O / Si) calculated from FIG. 3 against sputtering time.

[0011] Unless otherwise specified, "gas barrier properties" herein refer to the ability to barrier gases other than water vapor. Furthermore, in this specification, the term "barrier properties" refers to both gas barrier properties and water vapor barrier properties. The ability to maintain high barrier properties even when subjected to physical stress such as bending is sometimes referred to as "flex resistance." Furthermore, when describing layer structures, " / " indicates direct lamination, and " / / " indicates lamination either directly or via an adhesive layer. The term "outermost layer" does not refer to the layer present on the front side, distinguishing between the front and back sides. In other words, a vapor-deposited film or multilayer structure consisting of two or more layers has two outermost layers: one on one side and the other on the other side. Furthermore, in structures with a distinct inside and outside, such as a bag or container, the innermost layer is sometimes referred to as the innermost layer, and the outermost layer is sometimes referred to as the outermost layer. The term "major component" refers to the component with the highest content by mass. In this specification, the "thickness" of a layer or film refers to the average value of thicknesses measured at any five points.

[0012] <Vapor-deposited film> The vapor-deposited film of the present invention is a vapor-deposited film (X) comprising an ethylene-vinyl alcohol copolymer layer (A) and a vapor-deposited layer (B) made of silicon oxide or a metal oxide, in which the vapor-deposited layer (B) having a thickness of 30 nm or more and 200 nm or less is formed directly on the surface of the ethylene-vinyl alcohol copolymer layer (A), and when the surface of the vapor-deposited layer (B) facing the ethylene-vinyl alcohol copolymer layer (A) is designated as surface (b1) and the surface opposite to the vapor-deposited layer (B) is designated as surface (b2), elemental analysis of the vapor-deposited layer (B) in the depth direction from surface (b2) to surface (b1) using a scanning X-ray photoelectron spectrometer reveals that the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) in surface (b1) is ｂ１ and the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) at positions equidistant from the surface (b1) and the surface (b2). ｃ The ratio [(O / M) ｂ１ / (O / M) ｃ ] is 1.1 or more and 1.7 or less.

[0013] The vapor-deposited film (X) of the present invention has excellent gas barrier properties and flex resistance. The reason for this is unclear, but the following reason is presumed. In the vapor-deposited film (X), oxygen atoms segregate near the interface between the ethylene-vinyl alcohol copolymer layer (A) and the vapor-deposited layer (B), which is thought to increase the adhesion strength between the ethylene-vinyl alcohol copolymer layer (A) and the vapor-deposited layer (B). As a result, even when the vapor-deposited film is subjected to a flexing treatment, the ethylene-vinyl alcohol copolymer layer (A) maintains strong adhesion to the vapor-deposited layer (B), and it is presumed that a decrease in the gas barrier property after the flexing treatment is suppressed.

[0014] (Ethylene-Vinyl Alcohol Copolymer Layer (A)) The ethylene-vinyl alcohol copolymer layer (A) contains an ethylene-vinyl alcohol copolymer (hereinafter, sometimes referred to as EVOH) as a main component. The ethylene-vinyl alcohol copolymer is usually obtained by saponifying a copolymer of ethylene and a vinyl ester such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, or vinyl versatate. The production and saponification of the copolymer of ethylene and a vinyl ester can be carried out by known methods. The saponification degree of the vinyl ester component of the ethylene-vinyl alcohol copolymer is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. By setting the saponification degree to 90 mol% or more, the gas barrier property can be improved. The saponification degree of the ethylene-vinyl alcohol copolymer may be 100 mol% or less, or may be 99.99 mol% or less. The saponification degree of the ethylene-vinyl alcohol copolymer can be measured by nuclear magnetic resonance ( １ H-NMR measurement is performed to measure the peak area of ​​the hydrogen atoms contained in the vinyl ester structure and the peak area of ​​the hydrogen atoms contained in the vinyl alcohol structure.

[0015] The ethylene unit content of the ethylene-vinyl alcohol copolymer is preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, and even more preferably 25 mol% or more. Furthermore, the ethylene unit content of the ethylene-vinyl alcohol copolymer is preferably 65 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less. When the ethylene unit content is 10 mol% or more, the gas barrier property and flex resistance tend to be maintained well under high humidity. On the other hand, when the ethylene unit content is 65 mol% or less, the gas barrier property can be improved. The ethylene unit content of the ethylene-vinyl alcohol copolymer can be determined by NMR.

[0016] Furthermore, the ethylene-vinyl alcohol copolymer may contain units derived from other monomers other than ethylene, vinyl esters, and saponified products thereof, as long as the object of the present invention is not impaired. When the ethylene-vinyl alcohol copolymer contains the other monomer units, the content of the other monomer units relative to the total monomer units of the ethylene-vinyl alcohol copolymer is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less. When the ethylene-vinyl alcohol copolymer contains the units derived from the other monomers, the lower limit may be 0.05 mol% or 0.10 mol%. Examples of the other monomers include alkenes such as propylene, butylene, pentene, and hexene; 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl-1-butene, and 4-acyloxy-3-methyl- 1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene, 1,3-diacetoxy-2-methylenepentene unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, or the like, or their anhydrides, salts, or mono- or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methallylsulfonic acid, or salts thereof; vinyl silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, and the like.

[0017] When the ethylene-vinyl alcohol copolymer is a blend of two or more different types of ethylene-vinyl alcohol copolymers, the average ethylene unit content or saponification degree of the entire ethylene-vinyl alcohol copolymer is defined as the ethylene unit content or saponification degree of the ethylene-vinyl alcohol copolymer.

[0018] The MFR (190° C., 2.16 kg load) of the ethylene-vinyl alcohol copolymer 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.

[0019] The lower limit of the proportion of the ethylene-vinyl alcohol copolymer in the resin constituting the ethylene-vinyl alcohol copolymer layer (A) is preferably 70 mass %, more preferably 80 mass %, and even more preferably 90 mass %, from the viewpoint of gas barrier properties and the like, and may be 95 mass %, 99 mass %, 99.9 mass %, or 100 mass %.

[0020] The lower limit of the content of the ethylene-vinyl alcohol copolymer in the ethylene-vinyl alcohol copolymer layer (A) is preferably 70% by mass, more preferably 80% by mass, and even more preferably 90% by mass, and may be 95%, 99%, or 99.9% by mass, from the viewpoint of gas barrier properties, etc. The upper limit of the content of the ethylene-vinyl alcohol copolymer in the ethylene-vinyl alcohol copolymer layer (A) may be 100% by mass or 99.99% by mass.

[0021] The ethylene-vinyl alcohol copolymer layer (A) may contain inorganic oxide particles as needed. The inorganic oxide constituting the inorganic oxide particles is not particularly limited, but examples thereof include silicon oxide, aluminum oxide, magnesium oxide, zirconium oxide, cerium oxide, tungsten oxide, molybdenum oxide, and composites thereof. Among these, silicon oxide or silicon oxide-magnesium oxide is preferred, and silicon oxide is more preferred.

[0022] The lower limit of the content of inorganic oxide particles in the ethylene-vinyl alcohol copolymer layer (A) is preferably 0.001% by mass, more preferably 0.005% by mass, and even more preferably 0.01% by mass. The upper limit of the content of inorganic oxide particles is preferably 1% by mass, more preferably 0.7% by mass, and even more preferably 0.5% by mass. When the content of inorganic oxide particles is within the above range, the gas barrier property tends to be further improved.

[0023] The average particle size of the inorganic oxide particles is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less. When the average particle size of the inorganic oxide particles is within the above range, the gas barrier property tends to be further improved. The average particle size of the inorganic oxide particles is the d50 value measured by a laser diffraction scattering method.

[0024] The ethylene-vinyl alcohol copolymer layer (A) may further contain boron compounds, carboxylic acids, phosphorus compounds, metal ions, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, and the like, and may contain two or more of these optional components.

[0025] The ethylene-vinyl alcohol copolymer layer (A) may be an unstretched layer or a stretched layer, but from the viewpoints of dimensional stability and gas barrier properties, a layer stretched at least uniaxially is preferred, and a layer stretched biaxially is more preferred. From the viewpoints of thickness uniformity, barrier properties, mechanical properties, and film-formability, the stretching ratio is preferably 2.5 to 4.5 times in the machine direction (MD direction), 2.5 to 4.5 times in the transverse direction (TD direction), and an areal stretching ratio of 7 to 15 times, more preferably 2.5 to 3.5 times in the machine direction, 2.5 to 3.5 times in the transverse direction, and an areal stretching ratio of 8 to 12 times. Such a stretching treatment method can be carried out according to a known method such as commonly used simultaneous biaxial stretching or sequential biaxial stretching.

[0026] The thickness of the ethylene-vinyl alcohol copolymer layer (A) is not particularly limited, but is preferably 1 μm or more and 100 μm or less. When the thickness of the ethylene-vinyl alcohol copolymer layer (A) is 1 μm or more, the gas barrier properties of the vapor-deposited film are improved. The thickness of the ethylene-vinyl alcohol copolymer layer (A) is more preferably 2 μm or more, and even more preferably 3 μm or more. When the substrate film consists of only a single layer of ethylene-vinyl alcohol copolymer, the thickness of the ethylene-vinyl alcohol copolymer layer (A) is preferably 5 μm or more, more preferably 8 μm or more, and even more preferably 10 μm or more, from the viewpoint of handleability. When the ethylene-vinyl alcohol copolymer layer (A) is thin, it is preferable to form a multilayer film by co-extrusion molding the ethylene-vinyl alcohol copolymer with other resins, and then stretching the multilayer film as necessary to form the ethylene-vinyl alcohol copolymer layer (A). Furthermore, when the thickness of the ethylene-vinyl alcohol copolymer layer (A) is 100 μm or less, a flexible vapor-deposited film can be obtained. The thickness of the ethylene-vinyl alcohol copolymer layer (A) is more preferably 50 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The "thickness" refers to the average value of values ​​measured at any five points, and the same applies to the thicknesses of other layers described in this specification.

[0027] The oxygen permeability of the ethylene-vinyl alcohol copolymer layer (A) is 50 mL 20 μm / (m ２ ·day·atm) or less, and 10mL·20μm / (m ２ ·day·atm) or less is more preferable, and 5 mL ·20 μm / (m ２ ·day·atm) or less is more preferable, and 1 mL·20 μm / (m ２ Here, the oxygen permeability is a value measured on a film having a thickness of 20 μm under conditions of 20° C. and 65% RH in accordance with the method described in ISO 14663-2 Annex C (1999).

[0028] (Vapor-Deposited Layer (B)) The vapor-deposited layer (B) made of silicon oxide or a metal oxide can be effectively formed, for example, by using a vacuum deposition method. For example, when vacuum-depositing silicon oxide or a metal oxide onto a resin film that will become the ethylene-vinyl alcohol copolymer layer (A), it is important to perform the deposition while supplying an appropriate amount of oxygen gas toward the resin film. This results in the formation of a vapor-deposited layer (B) in which oxygen elements are segregated near the interface with the ethylene-vinyl alcohol copolymer layer (A). The degree of segregation can be controlled by, for example, the supply amount of oxygen gas sprayed onto the resin film. The supply amount of oxygen gas to the resin film is, for example, preferably 0.1 mL / min to 10 mL / min, more preferably 0.2 mL / min to 5 mL / min, and even more preferably 0.3 mL / min to 1 mL / min. However, the suitable supply amount of oxygen gas is appropriately adjusted depending on conditions such as the deposition rate of silicon oxide or metal oxide. The vapor-deposited layer (B) in which oxygen elements are segregated may also be formed by a vapor deposition method other than those described above. For example, the vapor deposition layer (B) may be provided by sputtering, ion plating, ion beam mixing, plasma CVD, laser CVD, MO-CVD, thermal CVD, or the like.

[0029] Before vapor deposition, the surface of the ethylene-vinyl alcohol copolymer layer (A) to be vapor-deposited may be plasma-treated. A known method can be used for the plasma treatment, and atmospheric pressure plasma treatment is preferred. Examples of discharge gases used in atmospheric pressure plasma treatment include nitrogen gas, helium, neon, argon, krypton, xenon, and radon.

[0030] Silicon oxide or metal oxide (MO Ｘ The vapor deposition layer (B) is made of silicon oxide (SiO Ｘ ) or a metal oxide. Here, M represents silicon or a metal element. The metal oxide is aluminum oxide (AlO Ｘ), magnesium oxide, calcium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, etc. Among these, a vapor deposition layer made of aluminum oxide or silicon oxide is preferred, and a vapor deposition layer made of silicon oxide is more preferred. Ｘ By providing the vapor-deposited layer (B) made of the above-mentioned fluororesin, the resulting vapor-deposited film (X) has excellent radio wave transmittance.

[0031] In the vapor-deposited film (X) of the present invention, when the surface of the vapor-deposited layer (B) on the ethylene-vinyl alcohol copolymer layer (A) side is designated as surface (b1) and the surface opposite to the vapor-deposited layer (B) is designated as surface (b2), and elemental analysis of the vapor-deposited layer (B) is performed in the depth direction from surface (b2) to surface (b1) using a scanning X-ray photoelectron spectrometer, the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) in surface (b1) is ｂ１ and the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) at positions equidistant from the surface (b1) and the surface (b2). ｃ The ratio [(O / M) ｂ１ / (O / M) ｃ The most notable feature is that the value of [Ratio of Ratio of ] is 1.1 or more and 1.7 or less.

[0032] Hereinafter, with reference to FIGS. 1 to 4, elemental analysis of the vapor-deposited layer (B) in the depth direction using a scanning X-ray photoelectron spectrometer will be described. FIG. 1 is a graph plotting the molar ratios of silicon (Si), oxygen (O), and carbon (C) (total 100 mol%) versus sputtering time when the vapor-deposited layer (B) formed in Example 2 was analyzed using a scanning X-ray photoelectron spectrometer. FIG. 2 is a graph plotting the molar ratio (O / Si) calculated from FIG. 1 versus sputtering time. The sputtering time of 0 minutes corresponds to the outermost surface of the vapor-deposited layer (B) and corresponds to surface (b2). Near surface (b2) exposed to the outside air, C and O increase due to the adsorption and oxidation of organic matter. Meanwhile, the composition of the vapor-deposited layer (B) near surface (b1) in contact with the ethylene-vinyl alcohol copolymer layer (A) also becomes unstable due to the influence of the ethylene-vinyl alcohol copolymer layer (A). Therefore, the molar ratio (O / M) at a position (center) equidistant from surface (b1) and surface (b2) ｃwas adopted as the reference value. Since the etching rate of the vapor-deposited layer (B) is considered to be nearly constant, the "position equidistant from surface (b1) and surface (b2)" corresponds to half of the sputtering time of surface (b1). Surface (b1) corresponds to the time when the proportion of carbon elements derived from the ethylene-vinyl alcohol copolymer layer (A) reaches 1 mol %, indicating the point at which the influence of the substrate begins. The vapor-deposited film of Example 2 is characterized by an increase in the oxygen concentration in the vapor-deposited layer (B) near surface (b1), since the film was formed while oxygen was supplied near the surface of the ethylene-vinyl alcohol copolymer layer (A) of the substrate.

[0033] The ratio calculated in this way [(O / M) ｂ１ / (O / M) ｃ When the ratio [(O / M) ｂ１ / (O / M) ｃ ] is large means that the oxygen content in the vapor-deposited layer (B) is high near the interface between the ethylene-vinyl alcohol copolymer layer (A) and the vapor-deposited layer (B), which is presumably to improve the adhesion between the ethylene-vinyl alcohol copolymer layer (A) and the vapor-deposited layer (B) and make the gas barrier property less likely to decrease even after bending treatment. As will be shown in the Examples below, when the film substrate is polyester or polyamide, the ratio [(O / M) ｂ１ / (O / M) ｃ The ratio [(O / M)] was less than 1.1, and the gas barrier properties after bending treatment were insufficient. This suggests that the state of oxygen present near the interface with the substrate changes depending on the substrate, and the oxidation degree of the vapor-deposited layer (B) changes. ｂ１ / (O / M) ｃ ] is preferably 1.13 or more, more preferably 1.15 or more. ｂ１ / (O / M) ｃ When the ratio [(O / M) ] is 1.7 or less, the vapor deposition layer (B) has excellent transparency and radio wave transmittance. ｂ１ / (O / M) ｃ] is preferably 1.5 or less, more preferably 1.3 or less.

[0034] The molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) in the surface (b1) ｂ１ The molar ratio (O / M) is preferably 1.85 or more and 2.35 or less. ｂ１ When the molar ratio (O / M) is 1.85 or more, the adhesion between the vapor-deposited layer (B) and the ethylene-vinyl alcohol copolymer layer (A) is improved, and a decrease in the gas barrier property after bending treatment can be suppressed. ｂ１ is more preferably 1.95 or more, even more preferably 2.0 or more, and particularly preferably 2.05 or more. ｂ１ When the molar ratio (O / M) is 2.35 or less, a homogeneous vapor-deposited layer (B) can be formed. ｂ１ is more preferably 2.3 or less.

[0035] In addition, the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) at positions equidistant from the surface (b1) and the surface (b2) is ｃ The molar ratio (O / M) is preferably 1.5 or more and 2.0 or less. ｃ When the molar ratio (O / M) is 1.5 or more, the vapor deposition layer (B) has excellent transparency and radio wave transmittance. ｃ is more preferably 1.55 or more, even more preferably 1.6 or more, and particularly preferably 1.65 or more, and in some cases 1.80 or more is preferable, and in other cases 1.81 or more is preferable. ｃ is 2.0 or less, (O / M) ｂ１ It becomes easier to increase the difference between the molar ratio (O / M) and the ｃ is more preferably 1.95 or less, and even more preferably 1.9 or less.

[0036] The thickness of the vapor-deposited layer (B) is 30 nm or more and 200 nm or less. The lower limit of the thickness of the vapor-deposited layer (B) is preferably 40 nm, more preferably 50 nm. When the thickness of the vapor-deposited layer (B) is equal to or greater than the above lower limit, the gas barrier properties and flex resistance of the vapor-deposited film can be further improved. The upper limit of the thickness of the vapor-deposited layer (B) is preferably 180 nm, and may be 160 nm or 140 nm.

[0037] The thickness of the vapor-deposited film (X) of the present invention is not particularly limited, and the lower limit may be, for example, 5 μm, 8 μm, or 10 μm, while the upper limit may be, for example, 100 μm, 50 μm, 30 μm, or 20 μm.

[0038] The oxygen permeability of the vapor-deposited film (X) of the present invention is 1.0 mL / (m ２ ·day·atm), and preferably less than 0.10 mL / (m ２ ·day·atm), and more preferably less than 0.05 mL / (m ２ ·day·atm), and more preferably less than 0.01 mL / (m ２ It is particularly preferable that the oxygen permeability is less than the above upper limit, so that the material can be particularly suitably used as various packaging materials. On the other hand, the lower limit of the oxygen permeability is 0 mL / (m ２ ·day·atm), and 0.001 mL / (m ２ The oxygen permeability of the vapor-deposited film (X) is a value measured under conditions of 20°C and 65% RH in accordance with the method described in ISO 14663-2 Annex C (1999).

[0039] The vapor-deposited film (X) of the present invention has excellent gas barrier properties and flex resistance. Furthermore, the vapor-deposited film (X) also has good radio wave transmittance. Therefore, the vapor-deposited film (X) can be used in a variety of applications. Examples of applications of the vapor-deposited film (X) include various packaging materials such as food packaging, pharmaceutical packaging, industrial chemical packaging, and pesticide packaging, as well as vacuum packaging bags and vacuum insulators. Taking advantage of its radio wave transmittance, the film is also useful as a packaging material for storing articles with RFID tags attached thereto.

[0040] <Multilayer Structure> The vapor-deposited film (X) of the present invention can also be suitably used as a multilayer structure in which other layers are further laminated.

[0041] (Polyolefin Layer (C)) A multilayer structure according to one embodiment of the present invention is a multilayer structure obtained by laminating the vapor-deposited film (X) of the present invention and a polyolefin layer (C). That is, the multilayer structure comprises a vapor-deposited film (X) and a polyolefin layer (C) laminated on at least one surface of the vapor-deposited film (X) directly or via another layer. When the multilayer structure comprises the vapor-deposited film (X) and the polyolefin layer (C), it is possible to improve not only the gas barrier property but also the water vapor barrier property. Furthermore, when the polyolefin layer (C) is the outermost layer of the multilayer structure, it can be easily molded into a shape such as a bag by, for example, heat-sealing the polyolefin layer (C) as a heat-sealing layer. In the multilayer structure of the present invention, the polyolefin layer (C) may be the innermost layer when formed into a bag.

[0042] The polyolefin layer (C) may be laminated directly to the vapor-deposited film (X) of the present invention, or may be laminated via another layer. Examples of the other layer include an adhesive layer. Examples of the adhesive layer include a layer made of a curing adhesive (such as a two-component reactive polyurethane adhesive).

[0043] The polyolefin constituting the polyolefin layer (C) is preferably polyethylene or polypropylene.

[0044] The polyolefin layer (C) may be a non-stretched layer or a stretched layer. In the multilayer structure of the present invention, when the multilayer structure is formed into a bag shape and the innermost layer is the polyolefin layer (C), it is preferred that the innermost polyolefin layer (C) is a non-stretched layer from the viewpoint of good heat sealability.

[0045] The lower limit of the thickness of the polyolefin layer (C) is preferably 5 μm, more preferably 10 μm, and even more preferably 15 μm, and may be 20 μm, 30 μm, or 40 μm. When the thickness of the polyolefin layer (C) is equal to or greater than the above lower limit, sufficient moisture resistance can be exhibited. Furthermore, when the polyolefin layer (C) is the outermost layer, when the thickness of the polyolefin layer (C) is equal to or greater than the above lower limit, sufficient heat sealability can also be exhibited. The upper limit of the thickness of the polyolefin layer (C) is preferably 200 μm, more preferably 100 μm, and may be 60 μm or 40 μm. When the thickness of the polyolefin layer (C) is equal to or less than the above upper limit, the thickness of the multilayer structure can be reduced.

[0046] The polyolefin content in the polyolefin layer (C) 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, and even more preferably 97% by mass or more and 100% by mass or less. The polyolefin layer (C) may contain, as components other than polyolefin, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, resins other than polyolefins, and the like.

[0047] The polyolefin layer (C) may consist of a single layer or multiple layers.

[0048] (Another Vapor-Deposited Film (Y)) The multilayer structure of the present invention may further include another vapor-deposited film (Y) laminated directly or via another layer on the vapor-deposited film (X) of the present invention. In other words, the multilayer structure of the present invention may include a plurality of vapor-deposited films, at least one of which may be the vapor-deposited film (X) of the present invention. A preferred example of the vapor-deposited film (Y) is a vapor-deposited film (Y) comprising a polyester layer (D) and a vapor-deposited layer (E) made of silicon oxide or a metal oxide. Specifically, a preferred embodiment of the present invention is a multilayer structure formed by laminating, in this order, a vapor-deposited film (Y) comprising a polyester layer (D) and a vapor-deposited layer (E) made of silicon oxide or a metal oxide, a vapor-deposited film (X), and a polyolefin layer (C). Here, the polyester layer (D) is preferably a polyethylene terephthalate (PET) layer. The vapor-deposited layer (E) may be formed of a material similar to the vapor-deposited layer (B) and with a similar thickness. A multilayer structure comprising a plurality of vapor-deposited films has excellent gas barrier properties and flex resistance without impairing radio wave transmittance.

[0049] The vapor-deposited films may be laminated directly to each other or may be laminated via another layer. Examples of the other layer include an adhesive layer, a polyolefin layer (C), a polyamide layer (F) described later, etc., and among these, an adhesive layer is preferred. Multiple layers may be present between the vapor-deposited films.

[0050] (Polyamide Layer (F)) The multilayer structure of the present invention may further comprise a polyamide layer (F) laminated to the vapor-deposited film (X) directly or via another layer. Specifically, a preferred embodiment of the present invention is a multilayer structure in which a polyamide layer (F), a vapor-deposited film (X), and a polyolefin layer (C) are laminated in this order. By providing the multilayer structure with the polyamide layer (F), it is possible to further improve the gas barrier properties and the like, and also to improve puncture resistance.

[0051] The vapor-deposited film (X) and the polyamide layer (F) may be laminated directly or via another layer, such as an adhesive layer. A plurality of layers may be present between the plurality of vapor-deposited films.

[0052] The polyamide layer (F) is preferably at least one outermost layer in the multilayer structure. In the multilayer structure of the present invention, the layer that becomes the outermost layer when the multilayer structure is formed into a bag shape may be the polyamide layer (F). In one embodiment of the multilayer structure of the present invention, one outermost layer may be the polyolefin layer (C), and the other outermost layer may be the polyamide layer (F).

[0053] The polyamide layer (F) typically contains polyamide as a main component. Polyamide is a resin containing an amide bond. Polyamide can be obtained, for example, by ring-opening polymerization of a lactam having a three- or higher ring member, polycondensation of a polymerizable ω-amino acid, or polycondensation of a dibasic acid and a diamine. Examples of polyamides include polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryl lactam (nylon 12), polyethylenediamineadipamide (nylon 26), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecamide (nylon 612), polyoctamethyleneadipamide (nylon 86), polydecamethyleneadipamide (nylon 108), caprolactam / lauryl lactam copolymer (nylon 6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon 6 / 9), caprolactam / hexamethylene Examples of the polymerizable monomer include diammonium adipate copolymer (nylon 6 / 66), lauryllactam / 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), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (nylon 6T), and hexamethylene isophthalamide / terephthalamide copolymer (nylon 6I / 6T).

[0054] The polyamide content in the polyamide layer (F) 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, and even more preferably 97% by mass or more and 100% by mass or less. The polyamide layer (F) may contain, as components other than polyamide, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, resins other than polyamides, and the like.

[0055] The polyamide layer (F) may be a non-stretched layer or a stretched layer.

[0056] The lower limit of the thickness of the polyamide layer (F) is preferably 1 μm, more preferably 3 μm, even more preferably 5 μm, and even more preferably 10 μm. When the thickness of the polyamide layer (F) is equal to or greater than the above lower limit, gas barrier properties, bending resistance, puncture resistance, etc. can be improved. The upper limit of the thickness of the polyamide layer (F) is preferably 100 μm, more preferably 50 μm, and may be 30 μm. When the thickness of the polyamide layer (F) is equal to or less than the above upper limit, it is possible to reduce the thickness of the multilayer structure, etc.

[0057] The polyamide layer (F) may consist of a single layer or multiple layers.

[0058] The multilayer structure of the present invention may further include a polyolefin layer (C), a polyamide layer (F), and a vapor-deposited film (Y). A particularly preferred embodiment of the present invention is a multilayer structure comprising a polyamide layer (F), a vapor-deposited film (Y), a vapor-deposited film (X), and a polyolefin layer (C) laminated in this order.

[0059] (Other Layers) The multilayer structure of the present invention may have layers other than the vapor-deposited film (X), the vapor-deposited film (Y), the polyolefin layer (C), and the polyamide layer (F). Examples of the other layers include an adhesive layer and a layer of another thermoplastic resin.

[0060] When the multilayer structure of the present invention has an adhesive layer, the thickness of the adhesive layer is, for example, preferably from 0.1 μm to 10 μm, more preferably from 0.3 μm to 7 μm, and even more preferably from 0.5 μm to 5 μm. By setting the thickness of the adhesive layer within the above range, it is possible to achieve a reduction in the weight of the multilayer structure while exhibiting sufficient adhesiveness.

[0061] (Layer Structure) Examples of the layer structure of the multilayer structure of the present invention include: (1) ethylene-vinyl alcohol copolymer layer (A) / vapor-deposited layer (B) / / C (2) C / / ethylene-vinyl alcohol copolymer layer (A) / vapor-deposited layer (B) / / C (3) Y / / ethylene-vinyl alcohol copolymer layer (A) / vapor-deposited layer (B) / / C (4) Y / / vapor-deposited layer (B) / ethylene-vinyl alcohol copolymer layer (A) / / C (5) F / / ethylene-vinyl alcohol copolymer layer (A) / vapor-deposited layer (B) / / C (6) F / / vapor-deposited layer (B) / ethylene-vinyl alcohol copolymer layer (A) / / C (7) F / / Y / / ethylene-vinyl alcohol copolymer layer (A) / vapor-deposited layer (B) / / C (8) F / / Y / / vapor-deposited layer (B) / ethylene-vinyl alcohol copolymer layer (A) / / C (9) F / / ethylene-vinyl alcohol copolymer layer (A) / vapor-deposited layer (B) / / Y / / C (10) F / / deposited layer (B) / ethylene-vinyl alcohol copolymer layer (A) / / Y / / C (11) Y / / F / / ethylene-vinyl alcohol copolymer layer (A) / deposited layer (B) / / C (12) Y / / F / / deposited layer (B) / ethylene-vinyl alcohol copolymer layer (A) / / C (13) Y / / Y / / ethylene-vinyl alcohol copolymer layer (A) / deposited layer (B) / / C (14) Y / / Y / / deposited layer (B) / ethylene-vinyl alcohol copolymer layer (A) / / C In addition, Y is a deposited film in which a deposited layer (E) is directly laminated on a polyester layer (D) (the orientation of the deposited film is not particularly limited), C is a polyolefin layer, and F is a polyamide layer.

[0062] The lower limit of the thickness of the multilayer structure of the present invention (the thickness of the entire multilayer structure) is preferably 10 μm, and may be 20 μm, 30 μm, or 50 μm. When the thickness of the multilayer structure is equal to or greater than the above lower limit, the gas barrier property and flex resistance can be further improved. The upper limit of the thickness of the multilayer structure is preferably 1,000 μm, and may be 500 μm, 300 μm, 200 μm, or 100 μm.

[0063] The method for producing the multilayer structure of the present invention is not particularly limited. For example, a multilayer structure can be obtained by laminating a polyolefin layer (C), a polyamide layer (F), another vapor-deposited film (Y), or the like, onto the vapor-deposited film (X) of the present invention by a known means such as dry lamination. Alternatively, a multilayer structure may be obtained by laminating a polyolefin layer (C), a polyamide layer (F), or the like onto the vapor-deposited film (X) of the present invention by, for example, melt extrusion.

[0064] The multilayer structure of the present invention can be used for various packaging materials such as food packaging, pharmaceutical packaging, industrial chemical packaging, and agricultural chemical packaging, as well as vacuum insulation bags and vacuum insulators.

[0065] <Packaging Material> The packaging material of the present invention includes the vapor-deposited film (X) of the present invention or the multilayer structure of the present invention. The packaging material is used for packaging purposes, and its shape is not limited. The packaging material may be in the form of a sheet, or may be molded into a predetermined shape such as a bag. From the viewpoint of heat-sealing properties, it is preferable that the polyolefin layer (C) is located in the outermost layer as a heat-sealable layer. From the viewpoint of heat-sealing properties, it is also preferable that the polyolefin layer (C) located in the outermost layer is not stretched. In the case of a packaging material molded into a shape having an inside and an outside, such as a bag, it is preferable that the polyolefin layer (C) is located at least in the innermost layer. It is also preferable that the vapor-deposited layer (B) is located outside the ethylene-vinyl alcohol copolymer layer (A). It is also preferable that a polyamide layer (F) is located in the outermost layer. Specific layer configurations preferred for packaging materials include "outside: (F) / / (B) / (A) / / (C): inside", etc.

[0066] The packaging material of the present invention is used for packaging, for example, foods, beverages, medicines, medical equipment, machine parts, clothing, etc. In particular, the packaging material is preferably used in applications requiring oxygen barrier properties and applications in which the interior of the packaging material is replaced with various functional gases. Because the packaging material includes the vapor-deposited film (X) of the present invention, deterioration of gas barrier properties after bending treatment is suppressed, and high gas barrier properties can be maintained over a long period of time. Taking advantage of its radio wave transmittance, the packaging material is also useful as a packaging material for containing an article equipped with an RFID tag inside. In other words, a package obtained by containing an article equipped with an RFID tag inside the packaging material of the present invention is also a preferred embodiment.

[0067] The packaging material is formed into various forms depending on the application, such as vertical form-fill-seal bags, spouted pouches, laminated tube containers, container lids, vacuum packaging bags, and the like.

[0068] Vertical form, fill, and seal pouches are used to package, for example, liquids, viscous materials, powders, bulk solids, and combinations of these foods and beverages. Vertical form, fill, and seal pouches are formed by heat-sealing a multilayer structure. When heat-sealing is performed, it is usually necessary to provide a heat-sealable layer (e.g., polyolefin layer (C)) on the layer of the multilayer structure that will become the inner layer of the vertical form, fill, and seal pouch, or on both the inner and outer layers of the vertical form, fill, and seal pouch. When the heat-sealable layer is only on the inner side of the vertical form, fill, and seal pouch, the body is usually sealed by seaming. When the heat-sealable layer is on both the inner and outer sides of the vertical form, fill, and seal pouch, the body is usually sealed by enveloping.

[0069] Spouted pouches are used to package liquid substances, such as liquid beverages such as soft drinks, jelly drinks, yogurt, fruit sauces, seasonings, functional water, liquid diets, etc. Laminated tube containers are used to package cosmetics, medicines, pharmaceuticals, food, toothpaste, etc. Container lids are lids for containers filled with foods such as processed meat products, processed vegetables, processed seafood products, and fruits.

[0070] <Vacuum Packaging Bag> The vacuum packaging bag of the present invention includes a packaging bag formed from the packaging material of the present invention, and the interior of the packaging bag is decompressed. The vacuum bag is useful for applications where vacuum packaging is desired, such as preserving food, beverages, etc., and as an outer packaging material for vacuum insulators. Because the vacuum packaging bag includes the vapor-deposited film (X) of the present invention, deterioration of gas barrier properties after bending treatment is suppressed, and a high vacuum state can be maintained for a long period of time. A multilayer structure suitable for use in a vacuum packaging bag preferably includes multiple vapor-deposited films (X). Furthermore, in cases where high mechanical strength is required, a multilayer structure preferably includes a polyamide layer (F). Examples of layer configurations of multilayer structures suitable for use in vacuum packaging bags include an outer layer (F) / / (Y) / / (B) / (A) / / (C) and an inner layer, and an outer layer (Y) / / (F) / / (B) / (A) / / (C) and an inner layer.

[0071] <Vacuum Insulator> The vacuum insulator of the present invention comprises the vacuum packaging bag of the present invention and a core material disposed inside the vacuum packaging bag. That is, a preferred embodiment of the vacuum insulator is one in which a core material is disposed inside the vacuum packaging bag and the inside is decompressed. In the vacuum insulator, the vacuum packaging bag is also referred to as an outer packaging material. Vacuum insulators are used for applications requiring cold insulation, heat insulation, etc. Examples of the core material include glass fiber and polyurethane foam. In the vacuum insulator, the core material is sealed in a vacuum state within the vacuum packaging bag (outer packaging material). The vacuum packaging bag (outer packaging material) is formed, for example, by heat-sealing a vapor-deposited film (X) or a multilayer structure.

[0072] The vacuum insulator of the present invention, because the vacuum packaging bag (outer packaging material) contains a vapor-deposited film (X), suppresses deterioration in gas barrier properties after bending and maintains high thermal insulation effects for a long period of time. This vacuum insulator can be used as an insulating material for home appliances such as refrigerators, hot water heaters, and rice cookers; residential insulating material used in walls, ceilings, attics, and floors; vehicle roofing; and insulating panels for vending machines. In particular, because the vacuum insulator is radio-transparent, it can be suitably used in various applications that apply RFID technology. For example, insulated boxes and the like made using the vacuum insulator of the present invention, it is possible to install contactless IC tags inside the boxes that can write information about the products stored therein, enabling the creation of efficient inventory management systems. In other words, a preferred embodiment of the present invention is a package in which an RFID-tagged item is housed inside a container surrounded by a vacuum insulator. It can also be used in various applications that apply IoT technology, which has become widespread in recent years and connects various objects, such as home appliances, cars, and buildings, to the Internet.

[0073] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. In the examples, " / " indicates that the two layers sandwiching the " / " are directly laminated together, and " / / " indicates that the two layers sandwiching the " / / " are laminated together via an adhesive.

[0074] [Materials used in Examples and Comparative Examples] EVOH-1: Biaxially stretched ethylene-vinyl alcohol copolymer film (ethylene unit content 32 mol%, saponification degree 99.9 mol%, thickness 12 μm) EVOH-2: Biaxially stretched ethylene-vinyl alcohol copolymer film (ethylene unit content 32 mol%, saponification degree 99.9 mol%, thickness 15 μm) EVOH-3: Unstretched ethylene-vinyl alcohol copolymer film (ethylene unit content 32 mol%, saponification degree 99.9 mol%, thickness 12 μm) OPET: "Lumirror (registered trademark) P60" (manufactured by Toray Industries, Inc., biaxially stretched PET film, thickness 12 μm) OPA: "Emblem (registered trademark) ONM15" (manufactured by Unitika Ltd., biaxially stretched polyamide film, thickness 15 μm) LLDPE: "Unilux (registered trademark) LS760C" (manufactured by Idemitsu Unitech Co., Ltd., linear low-density polyethylene film, thickness 50 μm) "Takelac (registered trademark) A520" (manufactured by Mitsui Chemicals, Inc., two-component polyurethane adhesive polyol component) "Takenate (registered trademark) A50" (manufactured by Mitsui Chemicals, Inc., two-component polyurethane adhesive isocyanate component) Barrier PET: "GL FILM (registered trademark) GL-AE" (manufactured by Toppan Printing Co., Ltd., aluminum oxide (40 nm) vapor-deposited biaxially stretched PET film, thickness 12 μm)

[0075] [Evaluation Method] (1) Molar Ratio (O / M) of Vapor Deposited Layer (B) The vapor deposited layer (B) made of silicon oxide or metal oxide in the vapor deposited films obtained in the Examples and Comparative Examples was subjected to elemental analysis while sputtering in the depth direction (from the surface (b2) side to the surface (b1) side) using a scanning X-ray photoelectron spectrometer "PHI Quntera SXM" manufactured by ULVAC-PHI, Inc. The X-ray source was AlKα (1486.6 eV), the X-ray beam diameter was 100 μmφ (25 W, 15 kV), the measurement range was 300 μm horizontal × 300 μm vertical, the signal acquisition angle was 45°, and the vacuum degree was 1×10 -６ The measurement was carried out under the condition of 100 Pa. The molar ratio of oxygen element (O) to silicon element or metal element (M) on the surface (b1) was (O / M). ｂ１The molar ratio of oxygen element (O) to silicon element or metal element (M) at a position equidistant from the surface (b1) and the surface (b2) is (O / M). ｃ and the ratio [(O / M) ｂ１ / (O / M) ｃ Here, the surface (b2) is the position where sputtering was started, the surface (b1) is the position where the content of carbon derived from the EVOH layer (A) reached 1 mol %, and a position equidistant from the surface (b1) and the surface (b2) was determined as the midpoint of the etching time.

[0076] (2) Oxygen Transmission Rate (OTR) of Vapor-Deposited Film A portion of the vapor-deposited film obtained in the Examples and Comparative Examples was cut out and measured using an oxygen transmission rate measuring device, OX-TRAN2 / 21 model (detection limit: 0.01 mL / (m ２ The OTR was measured using a 1000 mL / (m² / day·atm) solution under conditions of 20°C and 65% RH in accordance with the method described in ISO 14663-2 Annex C (1999), and evaluated according to the following criteria: A: 0.01 mL / (m² / day·atm) ２ · day · atm) (below detection limit) B: 0.01 mL / (m ２ ・day・atm) or more 0.05mL / (m ２ ・day・atm) C: 0.05mL / (m ２ ・day・atm) or more 0.10mL / (m ２ · day · atm) or less D: 0.10 mL / (m ２ ・day・atm) or more 1.0mL / (m ２ ・day・atm) or less E: 1.0 mL / (m ２ ・day・atm) or more

[0077] (3) Oxygen Transmission Rate (OTR) of Vapor-Deposited Films After Bending Test A 20 cm × 25 cm sample was cut from each of the vapor-deposited films obtained in the Examples and Comparative Examples, and a Gelbo Flex test (flexion test) was performed in accordance with ASTM F 392 using a Gelbo Flex Tester (BE-1005) manufactured by Tester Sangyo Co., Ltd. Specifically, the cut-out vapor-deposited film was shaped into a cylindrical shape with a diameter of 3.5 inches in an atmosphere of 23°C and 50% RH, and both ends were fixed to the Gelbo Flex Tester. The sample was subjected to three cycles of reciprocating motion, with an initial spacing of 7 inches, a maximum bending spacing of 1 inch, a 440° twist in the first 3.5 inches of the stroke, and a linear horizontal motion for the subsequent 2.5 inches. A portion of the bent portion of the vapor-deposited film after the bending test was cut out, and the oxygen transmission rate was measured and evaluated according to the method described in the evaluation method (2) above.

[0078] (4) Radio Wave Permeability Test (RFID Radio Wave Propagation) A 15 cm x 15 cm sample was cut from the vapor-deposited film obtained in the Examples and Comparative Examples, and the samples were overlapped with the resin substrate films facing each other. Three sides were heat-sealed at a width of 10 mm to produce a three-sided packaging bag. A UHF-band batteryless electronic paper tag manufactured by NETRONIX was filled into the opening of the resulting packaging bag and then sealed. From a position 20 cm away from the resulting packaging bag, it was confirmed whether the information on the IC tag could be read and written contactlessly using a UHF-band RF tag high-output handheld scanner SP-1 manufactured by Denso. Cases where the information could be read were evaluated as "A," and cases where the information could not be read were evaluated as "B."

[0079] (5) Oxygen Transmission Rate (OTR) of Multilayer Structure A portion of the multilayer structure obtained in each of the examples and comparative examples was cut out and measured using an oxygen transmission rate measuring device, OX-TRAN2 / 21 model (detection limit: 0.01 mL / (m ２ The OTR was measured using a test gas of 90% RH and a carrier gas of 0% RH at 40°C using a 1000 psi (1000 psi) / day atm (1000 psi) test gas at 90% RH and a carrier gas at 0% RH in accordance with the method described in ISO 14663-2 Annex C (1999), and evaluated according to the following criteria: A: 0.01 mL / (m ２ · day · atm) (below detection limit) B: 0.01 mL / (m ２・day・atm) or more 0.05mL / (m ２ ・day・atm) C: 0.05mL / (m ２ ・day・atm) or more 0.10mL / (m ２ · day · atm) or less D: 0.10 mL / (m ２ ・day・atm) or more 1.0mL / (m ２ ・day・atm) or less E: 1.0 mL / (m ２ ・day・atm) or more

[0080] (6) Oxygen Transmission Rate (OTR) of Multilayer Structure After Bending Test A 20 cm × 25 cm sample was cut from each of the multilayer structures obtained in the Examples and Comparative Examples, and a Gelbo Flex test (flex test) was performed in accordance with ASTM F 392 using a Gelbo Flex Tester (BE-1005) manufactured by Tester Sangyo Co., Ltd. Specifically, the cut-out vapor-deposited film was formed into a cylindrical shape with a diameter of 3.5 inches in an atmosphere of 23°C and 50% RH, and both ends were fixed to the Gelbo Flex Tester. The sample was subjected to three cycles of reciprocating motion, with an initial spacing of 7 inches, a maximum bending spacing of 1 inch, a 440° twist in the first 3.5 inches of the stroke, and a linear horizontal motion for the subsequent 2.5 inches. A portion of the bent portion of the vapor-deposited film after the bending test was cut out, and the oxygen transmission rate was measured and evaluated according to the method described in the evaluation method (5) above.

[0081] (7) Vacuum Insulator Radio Wave Permeability Test (RFID Radio Wave Propagation) 20 cm x 25 cm samples were cut from the multilayer structures obtained in the Examples and Comparative Examples, overlapped with the LLDPE facing each other, and heat-sealed on three sides at a width of 10 mm to produce a three-sided packaging bag. Glass fiber dried for 4 hours in an atmosphere of 160°C as a low thermal conductive core material and a small bag containing calcium oxide as an adsorbent were filled into the opening of the resulting packaging bag. The packaging bag was sealed at a temperature of 20°C and an internal pressure of 1.0 Pa using a vacuum insulation panel manufacturing device (KT-500RD model, manufactured by NPC Corporation) to produce a vacuum insulator. Two vacuum insulators thus obtained were closely attached to each other, and a NETRONIX UHF-band batteryless electronic paper tag was sandwiched between them. It was confirmed whether the information on the IC tag could be read and written contactlessly from a position 20 cm away from the surface of the vacuum insulator using a Denso UHF-band RF tag high-power handheld scanner SP-1. If the information could be read, it was evaluated as "A", and if it could not be read, it was evaluated as "B".

[0082] Example 1 A vapor deposition layer (B) made of silicon oxide was formed on EVOH-1 by the following method using a winding-type vacuum vapor deposition device "EWA-105" manufactured by Japan Vacuum Engineering Co., Ltd., which has a transfer chamber and a vapor deposition chamber. The "EWA-105" has an unwinder and a winder on the transfer chamber side, and silicon oxide (SiO Ｘ The chamber contained a crucible for heating the EVOH-1 film and a cooling can for cooling the film while transporting it, and the film was transported along the cooling can. The cooling can was cooled to -30°C, and a 120 cm wide EVOH-1 film was transported at a speed of 150 m / min. Furthermore, a nozzle for directly spraying oxygen onto the EVOH-1 before deposition was installed in the deposition chamber (nozzle gap 2 mm, film-nozzle distance 2 cm, angle relative to the film 30 degrees). Silicon oxide was vacuum-deposited while spraying oxygen at a rate of 0.38 mL / min, producing a deposited film in which a 40 nm-thick SiOx deposited layer (deposited layer (B)) was formed on the EVOH-1 film. The thickness of the deposited layer (B) was adjusted by appropriately controlling the voltage applied to the crucible. The obtained deposited film was evaluated according to the methods described in the above evaluation methods (1) to (4). The results are shown in Table 1.

[0083] [Examples 2 to 5, Comparative Example 1] Vapor-deposited films were prepared and evaluated in the same manner as in Example 1, except that the conveying speed of the biaxially stretched EVOH film during vapor deposition was changed so that the thickness of the vapor-deposited layer (B) made of silicon oxide was 60 nm (Example 2), 80 nm (Example 3), 100 nm (Example 4), 120 nm (Example 5), or 20 nm (Comparative Example 1). The results are shown in Table 1.

[0084] The vapor-deposited layer (B) formed in Example 2 was analyzed using a scanning X-ray photoelectron spectrometer, and the molar ratios of silicon (Si), oxygen (O), and carbon (C) (total 100 mol%) were plotted against sputtering time in a graph shown in Figure 1, while the molar ratio (O / Si) at that time was plotted against sputtering time in Figure 2. At the start of sputtering, carbon derived from organic contamination on the vapor-deposited film surface was detected on surface (b2), but after etching proceeded for about 0.5 minutes, carbon was no longer detected. As etching proceeded, carbon derived from the EVOH layer (A) of the substrate began to be detected, and at 6.01 minutes when the carbon content reached 1 mol%, surface (b1) was reached, and the molar ratio of oxygen element to silicon element (O / Si) at this time was ｂ１ In addition, at a sputtering time of 3.005 minutes, the molar ratio of oxygen element (O) to silicon element (Si) (O / Si) at positions equidistant from the surface (b1) and the surface (b2) was ｃ The ratio [(O / Si) ｂ１ / (O / Si) ｃ ] was 1.17, which indicated that the molar ratio (O / Si) was higher near the interface with the EVOH layer (A) than at the center of the vapor-deposited layer (B).

[0085] [Example 6] A vapor-deposited film was prepared and evaluated in the same manner as in Example 4, except that EVOH-2 was used instead of EVOH-1 as a biaxially stretched EVOH film and the thickness of the EVOH layer (A) was changed to 15 μm. The results are shown in Table 1.

[0086] Example 7 A deposited film was prepared and evaluated in the same manner as in Example 2, except that the supply rate of oxygen blown during deposition was changed to 0.19 mL / min. The results are shown in Table 1.

[0087] Example 8 A deposited film was prepared and evaluated in the same manner as in Example 2, except that the supply rate of oxygen blown during deposition was changed to 0.78 mL / min. The results are shown in Table 1.

[0088] Example 9 A vapor-deposited film was produced and evaluated in the same manner as in Example 4, except that the unstretched EVOH film EVOH-3 was used instead of the biaxially stretched EVOH film EVOH-1. The results are shown in Table 1.

[0089] [Example 10] Silicon oxide in the deposition chamber was replaced with aluminum oxide (AlO Ｘ ) was used, and a vapor-deposited film was prepared and evaluated in the same manner as in Example 2. The results are shown in Table 1.

[0090] [Comparative Examples 2 and 3] Vapor-deposited films were prepared and evaluated in the same manner as in Example 2, except that the biaxially stretched EVOH film EVOH-1 was replaced with the biaxially stretched PET film OPET (Comparative Example 2) or the biaxially stretched polyamide film OPA (Comparative Example 3). The results are shown in Table 1.

[0091] Comparative Example 4 A vapor-deposited film was produced and evaluated in the same manner as in Example 2, except that a biaxially stretched PET film OPET was used instead of the EVOH biaxially stretched film EVOH-1 and the oxygen supply rate blown during vapor deposition was changed to 0 mL / min. The results are shown in Table 1.

[0092] Comparative Example 5 A vapor-deposited film was prepared and evaluated in the same manner as in Example 2, except that the oxygen supply rate during vapor deposition was changed to 0 mL / min. The results are shown in Table 1. The vapor-deposited layer (B) formed in Comparative Example 5 was analyzed using a scanning X-ray photoelectron spectrometer. The molar ratios of silicon, oxygen, and carbon (total 100 mol%) were plotted against sputtering time in FIG. 3, and the molar ratio (O / Si) at that time was plotted against sputtering time in FIG. 4. Carbon derived from organic contamination on the vapor-deposited film surface was detected on surface (b2) at the start of sputtering, but carbon was no longer detected after etching proceeded for about 0.5 minutes. As etching proceeded, carbon derived from the EVOH layer (A) of the substrate began to be detected, and at 6.06 minutes, when the carbon content reached 1 mol%, surface (b1) was reached. At this time, the molar ratio of oxygen to silicon (O / Si)ｂ１ In addition, at a sputtering time of 3.03 minutes, the molar ratio of oxygen element (O) to silicon element (Si) (O / Si) at positions equidistant from the surface (b1) and the surface (b2) was ｃ The ratio [(O / Si) ｂ１ / (O / Si) ｃ ] was 1.08, which revealed that the molar ratio (O / Si) near the interface with the EVOH layer (A) was smaller than in Example 2 in which oxygen was supplied during deposition.

[0093] Comparative Example 6 An aluminum oxide vapor-deposited film was prepared and evaluated in the same manner as in Example 10, except that the supply rate of oxygen blown during vapor deposition was changed to 0 mL / min. The results are shown in Table 1.

[0094] Comparative Example 7: Aluminum oxide (AlO) in the deposition chamber Ｘ A vapor-deposited film was prepared and evaluated in the same manner as in Example 10, except that the metal (C) was changed to aluminum (Al). The results are shown in Table 1.

[0095] Comparative Example 8 A deposited film was prepared and evaluated in the same manner as in Example 2, except that the supply rate of oxygen blown during deposition was changed to 0.10 mL / min. The results are shown in Table 1.

[0096] Comparative Example 9 A vapor-deposited film was produced and evaluated in the same manner as in Example 10, except that the biaxially stretched EVOH film EVOH-1 was replaced with the biaxially stretched PET film OPET. The results are shown in Table 1.

[0097] A vapor-deposited film was produced and evaluated in the same manner as in Example 10, except that a biaxially stretched PET film OPET was used instead of the biaxially stretched EVOH film EVOH-1 and the oxygen supply rate blown during vapor deposition was changed to 0 mL / min. The results are shown in Table 1.

[0098]

[0099] Examples 11 to 13 Two-component adhesives (Takelac A-520 and Takenate A-50) were applied to one side of OPA, a biaxially oriented polyamide film, and then dried to form an adhesive layer. An adhesive layer was also formed in the same manner on the vapor-deposited surface of barrier PET, a biaxially oriented PET film vapor-deposited with aluminum oxide. An adhesive layer was also formed in the same manner on one side of LLDPE, a linear low-density polyethylene film. These three films were dry-laminated with the vapor-deposited film obtained in Example 1 (Example 11), the vapor-deposited film obtained in Example 2 (Example 12), or the vapor-deposited film obtained in Example 3 (Example 13) to prepare multilayer structures. The layer structure of the resulting multilayer structure was OPA / adhesive layer / barrier PET / adhesive layer / SiOx vapor-deposited layer (B) / EVOH-1 (A) / adhesive layer / LLDPE. The resulting multilayer structures were evaluated according to the evaluation methods (5) to (7) described above. The results are shown in Table 2.

[0100] A multilayer structure having a layer structure of OPA / adhesive layer / barrier PET / adhesive layer / Al-deposited layer / EVOH-1(A) / adhesive layer / LLDPE was prepared by dry laminating the film with the vapor-deposited film obtained in Comparative Example 7 instead of dry laminating it with the vapor-deposited film obtained in Example 1, and evaluated in the same manner as in Example 11. The results are shown in Table 2.

[0101] Example 14 A multilayer structure was produced and evaluated in the same manner as in Example 11, except that a multilayer structure having a layer structure of barrier PET / adhesive layer / SiOx vapor-deposited layer (B) / EVOH-1 (A) / adhesive layer / LLDPE was produced without laminating OPA. The results are shown in Table 2.

[0102]

Claims

1. A vapor-deposited film (X) comprising an ethylene-vinyl alcohol copolymer layer (A) and a vapor-deposited layer (B) made of silicon oxide or metal oxide, wherein the vapor-deposited layer (B) having a thickness of 30 nm or more and 200 nm or less is formed directly on the surface of the ethylene-vinyl alcohol copolymer layer (A), wherein the surface of the vapor-deposited layer (B) facing the ethylene-vinyl alcohol copolymer layer (A) is designated as surface (b1), and the surface opposite to the vapor-deposited layer (B) is designated as surface (b2), and when elemental analysis of the vapor-deposited layer (B) is performed in the depth direction from surface (b2) to surface (b1) using a scanning X-ray photoelectron spectrometer, the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) in surface (b1) is ｂ１ and the molar ratio (O / M) of oxygen element (O) to silicon element or metal element (M) at positions equidistant from the surface (b1) and the surface (b2). ｃ The ratio [(O / M) ｂ１ / (O / M) ｃ ] is 1.1 or more and 1.7 or less.

2. The vapor-deposited film (X) according to claim 1, wherein the ethylene-vinyl alcohol copolymer layer (A) is stretched at least uniaxially.

3. The vapor-deposited film (X) according to claim 1, wherein the thickness of the ethylene-vinyl alcohol copolymer layer (A) is from 1 μm to 100 μm.

4. The vapor-deposited film (X) according to claim 1, wherein the vapor-deposited layer (B) consists of silicon oxide or aluminum oxide.

5. The vapor-deposited film (X) according to claim 4, wherein the vapor-deposited layer (B) consists of silicon oxide.

6. The molar ratio (O / M) ｂ１ The vapor-deposited film (X) according to claim 1, wherein the refractive index is 1.85 or more and 2.35 or less.

7. The molar ratio (O / M) ｃ The vapor-deposited film (X) according to claim 1, wherein the σ is 1.5 or more and 2.0 or less.

8. A multilayer structure comprising the vapor-deposited film (X) according to any one of claims 1 to 7 and a polyolefin layer (C) laminated together.

9. The multilayer structure according to claim 8, which comprises a vapor-deposited film (Y) containing a polyester layer (D) and a vapor-deposited layer (E) made of silicon oxide or a metal oxide, a vapor-deposited film (X), and a polyolefin layer (C) laminated in this order.

10. The multilayer structure according to claim 8, which comprises a polyamide layer (F), a vapor-deposited film (X), and a polyolefin layer (C) laminated in this order.

11. The multilayer structure according to claim 10, which comprises a polyamide layer (F), a vapor-deposited film (Y), a vapor-deposited film (X), and a polyolefin layer (C) laminated in this order.

12. A packaging material comprising the multilayer structure of claim 8.

13. A package comprising the packaging material according to claim 12 and an article with an RFID tag attached thereto.

14. A vacuum packaging bag formed from the packaging material of claim 12.

15. A vacuum insulator in which a core material is placed inside the vacuum packaging bag according to claim 14, and the inside is decompressed.

16. A package comprising a container surrounded by the vacuum insulator of claim 15 and containing an item with an RFID tag attached thereto.

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