Laminates and packaging using the same

Abstract

To provide a laminate with excellent gas barrier property and a package using the laminate.SOLUTION: A laminate has a layer A on at least one side of a substrate film, the layer A contains at least aluminum (Al) and oxygen (O), and when an area of 5.0 to 25.0%, an area of 25.0 to 75.0%, and an area of 75.0 to 95.0% are defined as X-part, Y-part and Z-part respectively on the length reference in a depth direction on the layer A, an average composition ratio (O / Al)Z of aluminum (Al) and oxygen (O) in the Z-part and an average composition ratio (O / Al)Y in the Y-part fulfill (1) and (2) below. (1) (O / Al)Z≤2.0. (2) (O / Al)Y / (O / Al)Z≤1.2.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a laminate with excellent gas barrier properties and a packaging material using the same. [Background technology]

[0002] Various packaging materials have been used to package a wide range of items, including food and beverages, pharmaceuticals, and daily necessities. These packaging materials require oxygen barrier and water vapor barrier properties to prevent deterioration of the contents. Aluminum foil, which has excellent gas barrier properties, is used as a packaging material for retort foods. However, packaging materials using aluminum foil are difficult to handle because they are prone to pinholes, limiting their applications.

[0003] To solve these problems, films are used in which an inorganic compound layer, such as silicon dioxide or aluminum oxide, is formed on a substrate such as polyester film by physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, or ion plating, or by chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, or photochemical vapor deposition.

[0004] Methods for exhibiting gas barrier properties include controlling the composition of an inorganic compound layer made of aluminum oxide and the interface between that layer and the substrate it is in contact with (Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2003 / 009998 [Patent Document 2] Japanese Patent Publication No. 2017-177343 [Patent Document 3] International Publication No. 2014 / 050951 [Overview of the project] [Problems that the invention aims to solve]

[0006] All of these patent documents describe methods for controlling the composition and chemical state of a vapor-deposited layer composed of metal compounds.

[0007] Patent Document 1 relates to a technique for plasma pretreatment of a substrate and continuously changing the composition of the aluminum oxide vapor deposition layer laid on it from the substrate side to the surface. Patent Document 2 relates to a technique for improving the density of the vapor deposition layer by controlling the ratio of aluminum, aluminum oxide, and aluminum hydroxide as components in the aluminum oxide vapor deposition layer. Furthermore, Patent Document 3 relates to a technique for forming bonds at the interface between the substrate and the aluminum oxide vapor deposition layer, or for controlling the composition of the vapor deposition layer, by laminating the aluminum oxide vapor deposition layer on a plasma pretreatment substrate.

[0008] However, none of the patent documents described have optimized the components, composition, ratios, or structure of the vapor-deposited layer, and therefore have the drawback of being insufficient to achieve high gas barrier properties.

[0009] In view of this problem, the present invention aims to provide a laminate with excellent gas barrier properties and a packaging material using the same in a stable manner by clarifying the preferred state of the laminate. [Means for solving the problem]

[0010] The laminate of the present invention has a base film with a layer A on at least one side, and the layer A contains at least aluminum (Al) and oxygen (O). In the depth direction of the layer A, the area from 5.0 to 25.0% is defined as part X, the area from 25.0 to 75.0% as part Y, and the area from 75.0 to 95.0% as part Z, and when these areas are defined as part X, part Y, and part Z, respectively, the average composition ratio of aluminum (Al) to oxygen (O) in part Z when measured by X-ray photoelectron spectroscopy (XPS) is (O / Al). Z And the average composition ratio (O / Al) in section Y. Y However, it is a laminate that satisfies the following conditions (1) and (2). (1) (O / Al) Z ≤2.00 (2) (O / Al) Y / (O / Al) Z ≤1.20 Further, the A layer further contains hydrogen, and for the oxygen K-edge spectrum of electron energy loss spectroscopy (EELS) analysis in each of the X part, Y part, and Z part, the peak intensity near 530 eV is I X (530), I Y (530), I Z (530), and for the peak intensity near 540 eV of the oxygen K-edge spectrum of EELS analysis in each of the X part, Y part, and Z part in the A layer, it is I X (540), I Y (540), I Z (540), when I Y (530) / I Y (540)>I X (530) / I X (540) and / or I Y (530) / I Y (540)>I Z (530) / I Z (540), it is the laminate according to any one of the above.

[0011] Also, in the X part and Z part of the A layer, I X (530) / I X (540)≤0.15 and / or I Z (530) / I Z (540)≤0.25, it is the laminate according to any one of the above.

[0012] Also, the thickness of the A layer is 15.0 nm or less, it is the laminate according to any one of the above.

[0013] Also, the A layer contains hydrogen (H), and for the average composition of the A layer, the aluminum (Al) atom concentration: oxygen (O) atom concentration: hydrogen (H) atom concentration is 15.0 - 40.0:40.0 - 55.0:10.0 - 35.0 (atm%), it is the laminate according to any one of the above.

[0014] The laminate is further comprising a protective layer on the A layer, the protective layer further comprising a cured product containing a water-soluble resin and / or a metal alkoxide, as described above.

[0015] Furthermore, the protective layer is a laminate according to any of the above descriptions, further comprising a linear polysiloxane.

[0016] Furthermore, the present invention relates to a method for manufacturing a laminate according to any of the above, wherein aluminum is evaporated by vacuum deposition and oxygen is introduced into the aluminum vapor to form a deposited layer on at least one side of the substrate, and further to a method for manufacturing the same, wherein oxygen is introduced from the upstream and / or downstream side of the substrate.

[0017] Furthermore, it is a package containing the laminate described in any of the above. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a laminate with excellent gas barrier properties and a packaging material using the same. [Brief explanation of the drawing]

[0019] [Figure 1] This is a cross-sectional view showing an example of the laminate of the present invention. [Figure 2] This is a schematic diagram illustrating a roll-up type vacuum deposition apparatus for manufacturing the laminate of the present invention. [Figure 3] This is a schematic diagram illustrating an example of an oxygen gas introduction tube in a roll-up type vacuum deposition apparatus used for manufacturing laminates. [Figure 4] This is a schematic diagram illustrating an example of an oxygen gas introduction tube in a roll-up type vacuum deposition apparatus used for manufacturing laminates. [Figure 5] This is a schematic diagram illustrating an example of an oxygen gas introduction tube in a roll-up type vacuum deposition apparatus used for manufacturing laminates. [Modes for carrying out the invention]

[0020] The laminate of the present invention will be described in more detail below.

[0021] The laminate of the present invention has a base film with a layer A on at least one side, and the layer A contains at least aluminum (Al) and oxygen (O). In the depth direction of the layer A, the area from 5.0 to 25.0% is defined as part X, the area from 25.0 to 75.0% as part Y, and the area from 75.0 to 95.0% as part Z, and when these areas are defined as part X, part Y, and part Z, respectively, the average composition ratio of aluminum (Al) to oxygen (O) in part Z when measured by X-ray photoelectron spectroscopy (XPS) is (O / Al). Z And the average composition ratio (O / Al) in section Y. Y However, it is a laminate that satisfies the following conditions (1) and (2). (1) (O / Al) Z ≤2.00 (2) (O / Al) Y / (O / Al) Z ≤1.20 [Base film] The resin constituting the base film according to the present invention is not particularly limited and includes, for example, polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene; cyclic polyolefin resins; polyamide resins; polyimide resins; polyether resins; polyesteramide resins; polyether ester resins; acrylic resins; polyurethane resins; polycarbonate resins; or polyvinyl chloride resins; and even biodegradable resins such as polylactic acid, polycaprolactone, polyglycolic acid, and polyvinyl alcohol. Among these, polypropylene is preferred from the viewpoint of ease of recycling, and polyester is preferred from the viewpoint of adhesion to the inorganic layer and handling in addition to recyclability. It is preferable to include 3 to 55% by mass of recycled raw materials relative to the total amount of these resins. The recycled raw materials may be recycled by mechanical recycling or by chemical recycling, and are not particularly limited. Furthermore, the resin constituting the base film may be a mixed resin containing biomass-derived (plant-derived) raw materials and chemical fuel-derived raw materials. For example, in the case of polyester, it is preferable that either or both of the diol or dicarboxylic acid raw materials contain biomass-derived (plant-derived) raw materials in an amount of 10 to 95% by mass relative to the entire resin composition.

[0022] The base film may be unstretched or stretched (uniaxially or biaxially), but a biaxially stretched film is preferred from the viewpoint of thermal dimensional stability.

[0023] There are no particular restrictions on the thickness of the base film, but it is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 10 μm to 30 μm.

[0024] The surface of the base film on which layer A is formed may be pre-treated as needed to improve adhesion and smoothness, such as corona treatment, ozone treatment, plasma treatment, glow discharge treatment, ion beam treatment, ultraviolet treatment, solvent treatment, or formation of an anchor coat layer composed of organic or inorganic materials or mixtures thereof. Furthermore, on the opposite side of the surface on which layer A is formed, a coating layer of organic or inorganic materials or mixtures thereof may be laminated to improve the slipperiness during winding of the base film and to increase the scratch resistance of the base film.

[0025] [A layer] The A layer according to the present invention contains at least aluminum (Al) and oxygen (O), and in the depth direction of the A layer, the area from 5.0 to 25.0% of the length is defined as part X, the area from 25.0 to 75.0% as part Y, and the area from 75.0 to 95.0% as part Z, and when these areas are defined as part X, part Y, and part Z, respectively, the average composition ratio of aluminum (Al) to oxygen (O) in part Z measured by X-ray photoelectron spectroscopy (XPS) is (O / Al). Z And the average composition ratio (O / Al) in section Y. Y However, it must satisfy the following conditions (1) and (2). (1) (O / Al) Z ≤2.00 (2) (O / Al) Y / (O / Al) Z ≤1.20 The elements contained in layer A may include other elements as long as they contain at least aluminum (Al) and oxygen (O). For example, they may also contain hydrogen (H), carbon (C), nitrogen (N), silicon (Si), etc.

[0026] The statement that layer A contains aluminum (Al) and oxygen (O) means that, when evaluated by XPS (X-ray Photoelectron Spectroscopy; sometimes also known as ESCA (Electron Spectroscopy for Chemical Analysis)) under the conditions described in the examples, the elemental content ratio of each element is 5.0 atm% or more within 100.0 atm% of all atoms constituting layer A. Therefore, even if conditions (1) and (2) above are met, if the elemental content ratio of either aluminum (Al) or oxygen (O) within 100.0 atm% of all atoms constituting layer A is less than 5.0 atm%, it will be considered different from layer A of the present invention. The detailed evaluation conditions for the XPS method in the present invention are as described in the examples.

[0027] This method allows us to obtain a graph of the composition ratio with respect to depth. However, for example, if the laminate has a two-layer structure consisting of layer A and a substrate, the region up to 0.4 nm from the surface of layer A contains information about surface contamination. Therefore, the composition of layer A is calculated starting from a position deeper than 0.4 nm from the surface. Also, since the interface between layer A and the substrate is affected by the substrate, if the average carbon content of the substrate is C1 and the average carbon content of layer A is C2, the point at (C1 + C2) / 2 is used as the reference interface between layer A and the substrate, and the region from the reference interface to 0.4 nm from the surface is used as the measurement area for layer A in the XPS method. Unless otherwise specified, the average composition of layer A is calculated by averaging the measurement results at each measurement point in this measurement area. Specifically, first, a location that appears to be an interface is used as the reference interface between layer A and the substrate, and the average carbon content of layer A and the substrate is determined. The average carbon content of layer A and the substrate is then determined using the reference interface between layer A and the substrate derived from the calculated average carbon content. This process is repeated until the reference interface where the average carbon content converges is defined as the reference interface between layer A and the substrate. Furthermore, if there is an adjacent layer to layer A, such as when another layer is between layer A and the substrate, the reference interface is determined from the average carbon content of layer A and the adjacent layer using the same method as above. If there are adjacent layers on both sides of layer A, the respective reference interfaces determined in the same manner as above are used instead of the 0.4 nm surface layer.

[0028] When measuring using the XPS method, the X, Y, and Z regions of layer A are defined as follows: The X region refers to the area at 5.0-25.0% of the thickness of layer A as identified by the XPS method, based on length. The Y region refers to the area at 25.0-75.0% of the thickness of layer A from the center. Furthermore, the Z region refers to the area at 75.0-95.0% of the thickness. If the substrate can be identified, for example, if the laminate has a two-layer structure consisting of layer A and the substrate, the interface between layer A and the substrate side is set to 0%, and the outermost surface to 100%. If there is another layer between layer A and the substrate, the interface between layer A and that other layer is set to 0%. If there are multiple other layers, the interface between layer A and the adjacent layer and layer A is set to 0%. If there are adjacent layers on both sides of layer A, the interfaces with each adjacent layer are set to 0% and 100% as appropriate. In addition, the composition of each region is calculated by averaging the measurement results at each measurement point in each region.

[0029] Furthermore, in the EELS measurement described later, the X, Y, and Z regions of layer A are defined as follows: The X region refers to the area at 5.0-25.0% of the A layer thickness, as determined by cross-sectional observation images obtained by STEM (scanning transmission electron microscope), based on length. The Y region refers to the central 25.0-75.0% of the A layer thickness. The Z region refers to the area at 75.0-95.0% of the said thickness. Note that the A layer thickness is the value measured from cross-sectional observation images obtained by STEM (scanning transmission electron microscope), and if the substrate can be identified, for example, if the laminate has a two-layer structure consisting of layer A and the substrate, the interface between layer A and the substrate is set to 0%, and the outermost surface to 100%. If there is another layer between layer A and the substrate, the interface between layer A and that other layer is set to 0%. If there are multiple other layers, the interface between layer A and the adjacent layer and layer A is set to 0%. If there are adjacent layers on both sides of layer A, the interfaces with each adjacent layer are set to 0% and 100% as appropriate.

[0030] In the present invention, the average composition ratio of aluminum (Al) and oxygen (O) in the Z portion of layer A (O / Al) Z (O / Al) ZIt is hypothesized that when the ratio is ≤2.00, the number of unbonded bonds between aluminum (Al) and oxygen (O) decreases, making layer A denser and suppressing gas permeation in region Z, which is the inlet and outlet for gases such as oxygen and water vapor. Average composition ratio of aluminum (Al) to oxygen (O) in region Z of layer A (O / Al) Z is 2.00 < (O / Al) Z Therefore, we believe that the amount of aluminum peroxide in layer A increases, leading to the formation of a defective layer A, which reduces its gas barrier properties. The average composition ratio of aluminum (Al) to oxygen (O) in the Z region of layer A (O / Al) Z Preferably (O / Al) Z ≤1.90, more preferably (O / Al) Z ≤ 1.80. (O / Al) Z The lower limit is not specifically defined, but it corresponds to perfect aluminum oxide (alumina) (O / Al). Z If the ratio is 1.50, cracks and other problems may occur depending on the thickness of layer A, therefore (O / Al) Z By appropriately adjusting the thickness of layer A, or by further including hydrogen (H) in layer A as described later, the laminate of the present invention can be obtained. Z Even when the value is 1.5, the aluminum is not necessarily a perfect oxide; it may contain hydroxides, or possibly aluminum monoxide or aluminum peroxide. This is thought to be because moisture in the atmosphere during deposition, and even if moisture adhesion after deposition is prevented, residual moisture in the deposition tank or moisture contained in the substrate are incorporated into the film during or after deposition.

[0031] Furthermore, the above (O / Al) Z And the average composition ratio (O / Al) in section Y. Y This is the ratio (O / Al). Y / (O / Al) Z (O / Al) Y / (O / Al) ZIt is hypothesized that when the ratio is ≤1.20, the composition gradient in the depth direction of layer A is small, resulting in a uniform layer, which suppresses the diffusion of gases such as oxygen and water vapor within layer A. As a result, layer A becomes a dense and uniform film, and by suppressing gas permeation and diffusion, it can exhibit high gas barrier properties. (O / Al) Z And the average composition ratio (O / Al) in section Y. Y This is the ratio (O / Al). Y / (O / Al) Z 1.20 < (O / Al) Y / (O / Al) Z Conversely, if this is the case, the A layer will become a non-uniform film, making it easier for gas to be absorbed into the A layer and for it to permeate and diffuse, thus reducing the gas barrier properties. Also, the (O / Al) Z And the average composition ratio (O / Al) in section Y. Y This is the ratio (O / Al). Y / (O / Al) Z Preferably (O / Al) Y / (O / Al) Z ≤ 1.10, and there is no particular limit on the lower limit, but (O / Al) Y / (O / Al) Z If the ratio is <0.96, problems such as curling may occur depending on the thickness of layer A, therefore (O / Al) Y / (O / Al) Z By appropriately adjusting the thickness of layer A, or by further including hydrogen (H) in layer A as described later, the laminate of the present invention can be obtained.

[0032] Furthermore, if there are multiple layers containing aluminum (Al) and oxygen (O), the condition that at least one layer can become layer A of the present invention is met, and layer A contains at least aluminum (Al) and oxygen (O), and in the depth direction of layer A, the area from 5.0 to 25.0% of the length is defined as part X, the area from 25.0 to 75.0% as part Y, and the area from 75.0 to 95.0% as parts X, Y, and Z respectively, the average composition ratio of aluminum (Al) and oxygen (O) in part Z measured by X-ray photoelectron spectroscopy (XPS) is (O / Al). Z And the average composition ratio (O / Al) in section Y.Y However, the laminate is one that satisfies the following conditions (1) and (2). (1) (O / Al) Z ≤2.00 (2) (O / Al) Y / (O / Al) Z ≤1.20 A single layer refers to a region that has a distinguishable interface in the thickness direction, separate from adjacent regions, and has a finite thickness. More specifically, it refers to a region that is distinguishable by a discontinuous interface when the cross-section of layer A is observed with a scanning transmission electron microscope (STEM) as described in the examples. Even if the composition of layer A changes in the thickness direction, if there is no aforementioned interface between the layers, it is treated as a single layer.

[0033] Layer A contains at least aluminum (Al) and oxygen (O), and when X, Y, and Z sections are defined in the depth direction within layer A, it is preferable to appropriately adjust the position, amount, and method of introducing oxygen gas as a means of achieving the laminate of the present invention. Specifically, taking the winding-type vacuum deposition apparatus 3 shown in Figure 2 as an example, the amount of oxygen gas introduced during the formation of layer A is 5.0 × 10 -2 When aluminum is evaporated with a reduced pressure of Pa or less, a substrate transport speed of 400 m / min, a substrate width of 1.0 m, and a target thickness of 8 nm for layer A, it is preferable that the amount of oxygen gas introduced is 2 to 19 L / min. As for the method of introducing oxygen gas, it is preferable to use a tubular shape with a single introduction direction, as shown in Figure 4, from the viewpoint of introducing oxygen precisely to each of the X, Y, and Z sections. As shown in Figure 4, the tubular shape of the gas inlet allows for high directivity of the gas introduced from the inlet, enabling efficient oxidation of the targeted location. As shown in Figure 3, a pinhole shape allows the oxygen gas introduced from the inlet to permeate uniformly into the aluminum vapor, but from the viewpoint of pinpoint oxidation of the targeted location, it may be inferior to the tubular shape. It is also possible to use a tubular shape with multiple introduction directions, as shown in Figure 5, but controlling the gas introduction may become difficult.

[0034] As an example of a more preferable means of achieving this, it is preferable to highly activate the aluminum vapor and oxygen gas during deposition. There are various excitation methods for activation, such as plasma, ions, light, and heat, but plasma is preferred because it can activate relatively efficiently. Examples of plasma generation methods include hollow cathode discharge, microwave plasma, ICP plasma, and helicon wave plasma, but among these plasma generation methods, hollow cathode discharge is particularly preferred and suitable as a large-capacity plasma generation method. Hollow cathode discharge is a method that generates plasma in a hollow cathode, confines primary electrons in a sheath formed along the inner wall of the cavity, improves ionization efficiency, and generates a powerful plasma between the anode facing the opening of the cavity. Depending on the width and number of aluminum evaporation sources, about 5 hollow cathode plasma sources per meter are arranged in the width direction of the film to perform uniform activation in the width direction. As an example, in Figure 2, to activate the plasma that generates high-density plasma in the space between the evaporation source 15 and the transported substrate 1, the plasma source shown 21 is placed near the deposition source 15, and the plasma 22 is sent into the space between the deposition source 15 and the main drum 9, where it acts on and activates the gas and evaporated materials present in this region. Furthermore, the plasma also reaches the surface of the substrate 1 during deposition, promoting the deposition process.

[0035] The A layer of the present invention further contains hydrogen (H), and the peak intensity around 530 eV of the oxygen K-edge spectrum of electron energy loss spectroscopy (EELS) analysis in the X, Y, and Z regions is I X (530), I Y (530), I Z (530) The peak intensity around 540 eV of the oxygen K-edge spectrum of the EELS analysis in the X, Y, and Z regions of layer A is I X (540), I Y (540), I Z When (540), I Y (530) / I Y (540)>I X (530) / I X (540) and / or I Y(530) / I Y (540)>I Z (530) / I Z (540) is preferable.

[0036] EELS analysis is an electron energy loss spectroscopy (EELS) analysis technique that analyzes the elemental composition and chemical bonding state of a sample by injecting electrons into the sample and then spectroscopically analyzing the electrons (inelastically scattered electrons) that have lost energy due to their interaction with the sample. The inelastic scattering analyzed includes core electron excitations (50 eV and above), interband transitions due to valence electron excitations (0-10 eV), and plasmon excitations due to collective electron oscillations (10-50 eV). The oxygen K-edge spectrum refers to the absorption spectrum in the core electron region of the EELS spectrum. Note that I(530) refers to the peak intensity around 530 eV, which is the intensity of the peak top detected between 528.0 and 531.0 eV. However, if multiple peak tops are detected between 528.0 and 531.0 eV, the intensity of the peak top with the highest peak intensity is used. If no peak top is detected, the intensity at 530 eV is used. I(540) refers to the peak intensity around 540 eV, which is the intensity of the peak top detected between 535.0 and 545.0 eV. However, if multiple peak tops are detected between 535.0 and 545.0 eV, the intensity of the peak top with the highest peak intensity is used. If no peak top is detected, the intensity at 540 eV is used.

[0037] EELS analysis is measured by STEM-EELS (Scanning Transmission Electron Microscopy-Electron Energy Loss Spectroscopy). As a pretreatment of the sample before measuring STEM-EELS, the FIB method (Focused Ion Beam method) is used. Specifically, based on the method described in "Polymer Surface Processing Science" (written by Akira Iwamori), pp. 118-119, a cross-sectional observation sample is prepared using a micro-sampling system. At that time, the sample is handled entirely in a glove box (under a nitrogen atmosphere), except when carbon deposition is performed for the purpose of imparting conductivity to the surface. The detailed measurement conditions are as in the examples. By the aforementioned XPS method, the approximate positions of the layers containing aluminum (Al) and oxygen (O) are grasped, and the interfaces of those layers are grasped by STEM measurement. EELS measurement is performed on the X part, Y part, and Z part of the layer, and I(530) and I(540) of each part of the layer are obtained.

[0038] When there are multiple layers containing aluminum (Al) and oxygen (O), in at least one layer, I Y (530) / I Y (540)>I X (530) / I X (540) and / or I Y (530) / I Y (540)>I Z (530) / I Z (540), if so, the laminate has an A layer, and the A layer contains at least aluminum (Al) and oxygen (O), and further contains hydrogen (H). The peak intensity near 530 eV of the oxygen K-edge spectrum of the electron energy loss spectroscopy (EELS) analysis in each of the X part, Y part, and Z part is I X (530), I Y (530), I Z (530) is taken as, and the peak intensity near 540 eV of the oxygen K-edge spectrum of the EELS analysis in each of the X part, Y part, and Z part in the A layer is I X (540), I Y (540), I Z (540) is taken as, when I Y(530) / I Y (540)>I X (530) / I X (540) and / or I Y (530) / I Y (540)>I Z (530) / I Z (540)

[0039] In EELS analysis, the peak around 530 eV in the oxygen K-edge spectrum is derived from hydroxide, while the peak around 540 eV is a hybrid peak of Al and O. In other words, if we denote the peak intensities as I(530) and I(540), a larger value of I(530) / I(540) indicates a higher amount of hydroxide in the film, while a smaller value indicates a lower amount of hydroxide.

[0040] I Y (530) / I Y (540)>I X (530) / I X (540) and / or I Y (530) / I Y (540)>I Z (530) / I Z (540) indicates that the amount of hydroxide in the outer portion (X and / or Z) is less than that of the Y portion. The reduced amount of hydroxide in the outer portion (X and / or Z) compared to the Y portion results in higher density in the outer portion (X and / or Z), preventing gases such as oxygen and moisture from entering the A layer from the outside, and consequently achieving high gas barrier properties. From the viewpoint of the variations in film quality and barrier properties described above, I Y (530) / I Y (540)>I X (530) / I X (540) is more preferable, I Y (530) / I Y (540)>I X (530) / I X (540) and I Y (530) / I Y (540)>I Z (530) / IZ (540) is even more preferable.

[0041] As a means of achieving the above configuration, appropriate oxygen gas introduction position, amount, and introduction method can be used. The details are the same as described above, but taking the roll-up type vacuum deposition apparatus 3 shown in Figure 2 as an example, by using a tubular oxygen gas introduction pipe with an introduction direction in one direction as shown in Figure 4, and introducing more oxygen from the upstream side to the upstream side of the substrate, and / or introducing more oxygen from the upstream side directly above the evaporation source, compared to the case where this is not done, I X (530) / I X (540) can be lowered. By introducing more oxygen directly above the evaporation source, I can be lowered compared to the case where this is not done. Y (530) / I Y (540) can be reduced. By introducing more oxygen downstream of the substrate and / or introducing more oxygen directly above the evaporation source from the downstream side, I can be reduced compared to the case where this is not done. Z (530) / I Z (540) can be lowered. Also, by increasing the degree of decompression, i.e., lowering the ambient pressure, the overall value of I(530) / I(540) can be lowered.

[0042] The inclusion of hydrogen (H) in layer A means that, when evaluated by the HR-RBS / HR-HFS method under the conditions described in the examples, the average composition of layer A contains 5.0 atm% or more hydrogen. By including hydrogen (H), flexibility can be imparted to the laminate, thereby suppressing the occurrence of cracks and curls.

[0043] The total light transmittance of the laminate is preferably 85.0% or higher. A total light transmittance of 85.0% or higher ensures excellent visibility of the contents. Total light transmittance can be measured using a haze meter.

[0044] The A layer is formed on a film containing a substrate, and in the X and Z portions of the A layer, X (530) / I X(540) ≤ 0.15 and / or I Z (530) / I Z (540) ≤ 0.25 is preferable. X (530) / I X (540) ≤ 0.15 and / or I Z (530) / I Z Since (540) ≤ 0.25, the amount of hydroxide in the X region close to the substrate and / or the Z region far from the substrate is reduced, resulting in a dense film and thus good gas barrier properties. From the viewpoint of gas barrier properties, I X (530) / I X (540) ≤ 0.11 and / or I Z (530) / I Z (540) ≤ 0.20 is more preferable, I X (530) / I X (540) ≤ 0.083 and / or I Z (530) / I Z (540) ≤ 0.15 is even more preferable.

[0045] The thickness of layer A is preferably 15.0 nm or less. A thickness of 15.0 nm or less of layer A provides good barrier properties and excellent bending resistance. From a similar viewpoint, 10.0 nm or less is more preferable, 8.0 nm or less is even more preferable, and 7.0 nm or less is particularly preferable. The thickness of layer A can be measured from a cross-sectional observation image obtained by scanning transmission electron microscopy (STEM).

[0046] From the viewpoint of ensuring barrier properties and flexibility, it is preferable that the average composition of layer A has aluminum (Al) atom concentration: oxygen (O) atom concentration: hydrogen (H) atom concentration of 15.0~40.0:40.0~55.0:10.0~35.0 (atm%). The average composition of layer A shall be measured by the HR-RBS / HR-HFS method. The specific measurement conditions are as described in the examples. From a similar viewpoint, it is more preferable that the Al atom concentration: O atom concentration: H atom concentration is 20.0~35.0:40.0~55.0:15.0~30.0 (atm%). Furthermore, it is preferable that the concentrations of nitrogen (N) atoms and carbon (C) atoms are both 5 atm% or less.

[0047] [Example of a manufacturing method for layer A] There are no particular limitations on the method for forming layer A, and methods such as vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, atomic layer deposition, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD, laser CVD, thermal CVD, and coating can be used. From the viewpoint of manufacturing cost and gas barrier properties, vacuum deposition is preferred.

[0048] Layer A can be formed on at least one side of the substrate by evaporating aluminum using a vacuum deposition method and introducing oxygen into the aluminum vapor. Methods for evaporating aluminum using vacuum deposition include, but are not limited to, electron beam (EB) deposition, resistance heating, and induction heating. By adjusting the amount of aluminum evaporated using the aforementioned method and then introducing oxygen into the aluminum vapor, a layer A with controlled oxygen content and film quality can be obtained. As long as the gas introduced contains oxygen, it may also contain other gases, such as inert gases, to control film quality.

[0049] It is preferable to introduce oxygen from the upstream and / or downstream side of the substrate. It is preferable to introduce oxygen from the aforementioned position toward the direction of aluminum evaporation gas. By introducing oxygen as described above, the film quality of the X and / or Z portion of layer A is improved, and the barrier properties and adhesion are enhanced. It is more preferable to introduce oxygen from the upstream side of the substrate or from both the upstream and downstream sides of the substrate.

[0050] An example of a method for forming layer A using a winding-type vacuum deposition apparatus is shown in Figure 2. An aluminum oxide deposition layer is formed as layer A on the surface of the substrate 1 by electron beam (EB) heating deposition. First, aluminum granules are set in the evaporation source 15 as the deposition material. In the winding chamber 4, the side of the substrate 1 on which layer A will be deposited is set on the unwinding roll 5 so that it faces the evaporation source 15, and it is passed through the main drum 9 via unwinding guide rolls 6, 7, and 8. Next, the pressure inside the vacuum deposition apparatus 3 is reduced by a vacuum pump to 5.0 × 10⁻⁶ -3 A vacuum of less than Pa is obtained. The ultimate vacuum is 5.0 × 10⁻⁶. -3 A vacuum level of Pa or less is preferable. The ultimate vacuum level is 5.0 × 10⁻⁶. -2 By keeping the pressure below Pa, the residual gas in the vacuum deposition apparatus is reduced, improving the film quality of layer A. The temperature of the main drum 9 is set to -30°C as an example. From the viewpoint of preventing thermal damage to the substrate, a temperature of 20°C or lower is preferable, and more preferably 0°C or lower. Next, an electron gun (EB gun) 17 is used as a heating source to dissolve the aluminum in the evaporation source. After all the aluminum granules have melted, a linear anode layer type ion source 14 (Veeco, USA, ALS1000L), installed at a distance of 50 mm from the film running surface, is operated with an oxygen flow rate of 8 L / min, an anode voltage of 10 kV, and an anode current of 8.6 A to treat the substrate surface. Subsequently, the EB gun, acceleration current, film transport speed, and oxygen gas introduction amount are adjusted so that the thickness of the A layer to be formed is 5 nm, and layer A is formed on the surface of the substrate 1. Depending on the desired film quality, one or more oxygen gas introduction tubes 16a to c are used as the oxygen gas introduction position. As shown in Figure 4, the oxygen gas introduction tube is a tubular shape with introduction in one direction. From the viewpoint of improving the film quality in the initial stages of deposition and improving adhesion and barrier properties, it is preferable to use 16a and / or 16b. After that, it is wound onto the winding roll 13 via guide rolls 10, 11, and 12. The substrate surface treatment with the ion source and the deposition of layer A may be performed in the same transport or in separate transports.

[0051] Furthermore, in order to further activate the aluminum vapor and oxygen gas, the plasma source of the hollow cathode shown in 21 of Figure 2 may be placed near the deposition source 15, and the plasma may be sent into the space between the deposition source 15 and the main drum 9, and activated by acting on the gases and vapors present in this region.

[0052] [Protective layer] It is preferable to form a protective layer containing a cured product of a water-soluble resin and / or a metal alkoxide on the outermost surface of the laminate of the present invention, that is, on layer A. The outermost surface, as used herein, refers to the surface of layer A after it has been laminated onto the substrate. Having a protective layer containing the cured product can further improve gas barrier properties and impart scratch resistance, printability, retort resistance, etc.

[0053] Examples of water-soluble resins include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and modified polyvinyl alcohol. These resins may be used individually or as a mixture of two or more, but vinyl alcohol-based resins (including modified polyvinyl alcohol) are preferred. Vinyl alcohol-based resins (including modified polyvinyl alcohol) are generally obtained by saponifying polyvinyl acetate. This may be partial saponification, where only a portion of the acetate groups are saponified, or complete saponification, but a higher degree of saponification is preferred. The degree of saponification is preferably 90% or higher, and more preferably 95% or higher. If the degree of saponification is low and the resin contains many acetate groups with high steric hindrance, the free volume of the layer may increase. The degree of polymerization of the vinyl alcohol-based resin is preferably 1,000 to 3,000, and more preferably 1,000 to 2,000. When the degree of polymerization is low, the polymer is less likely to be fixed, and gas barrier properties are more likely to be exhibited.

[0054] Furthermore, a particularly preferred water-soluble resin is a vinyl resin having carbonyl groups in its cyclic structure. By including a vinyl resin having carbonyl groups in its cyclic structure as the water-soluble resin in the protective layer, the hydrophobicity due to the cyclic structure and the interaction around the resin due to the carbonyl groups result in a dense film structure, improving water resistance and creating a dense protective layer with low hydrophilicity. This reduces interaction with gas molecules such as oxygen and water vapor, blocking the permeation pathways of gas molecules, and thus exhibiting excellent gas barrier properties. In this invention, the vinyl resin having carbonyl groups in its cyclic structure is preferably present in an amount of 20 to 100% by mass of the total water-soluble resin in the protective layer. If it is less than 20% by mass, the effect of improving gas barrier properties may be poor, and 100% by mass, where all water-soluble resins are vinyl resins having carbonyl groups in their cyclic structure, is most preferable.

[0055] The cyclic structure is not particularly limited as long as it is a ring with three or more members (for example, a ring with three to six members). Furthermore, it may be a heterocyclic cyclic structure containing heteroatoms other than carbon, such as nitrogen, oxygen, sulfur, or phosphorus. The carbonyl group portion within this cyclic structure may be located in either the main chain, side chain, or crosslinking chain of the vinyl resin. Specific examples of vinyl resins having carbonyl groups in these cyclic structures include lactone structures, which are cyclic esters, and lactam structures, which are cyclic amides. These may be used individually or in combination of two or more, and are not particularly limited, but lactone structures are preferred. Using a vinyl resin having a lactone structure as a water-soluble resin makes it stable against the acid catalyst used for hydrolysis of silicon alkoxides (described later) and easier to maintain gas barrier properties. Examples of vinyl resins having a lactone structure include α-acetolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone.

[0056] Examples of metal alkoxides include titanium, aluminum, zirconium, and silicon, but silicon alkoxide is preferred in the present invention.

[0057] Silicon alkoxides are a type of metal alkoxide represented by Si(OR)4, where R is preferably a lower alkyl group, such as a methyl group, ethyl group, n-propyl group, or n-butyl group. Specific examples of silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which may be used individually, as a mixture of two or more, or as hydrolyzed products thereof, as described later.

[0058] The protective layer of the present invention preferably further contains linear polysiloxane. Because linear polysiloxane has few pores in its molecular chains and can exist at a high density with other molecular chains, including linear polysiloxane and forming a network within the protective layer allows for the suppression of the movement of molecular chains of the components constituting the protective layer. This results in a denser protective layer structure, which further improves the gas barrier properties and facilitates the manifestation of gas barrier properties.

[0059] A linear polysiloxane is represented by the following chemical formula (1), where n is an integer of 2 or more. In chemical formula (1), R can be a lower alkyl group such as a methyl group, ethyl group, n-propyl group, or n-butyl group, or a branched alkyl group such as an iso-propyl group or t-butyl group. In the present invention, a longer linear structure of the linear polysiloxane makes it easier to form a network and fix it in the protective layer, so n is preferably 5 or more, and more preferably 10 or more.

[0060] [ka]

[0061] Linear polysiloxanes can be obtained from silicon alkoxides represented by Si(OR)4, as described above. In silicon alkoxides, R is preferably a lower alkyl group, such as a methyl group, ethyl group, n-propyl group, or n-butyl group. Specific examples of silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which may be used individually or as a mixture of two or more. Silicon alkoxides can be hydrolyzed, for example, to obtain linear polysiloxanes. The silicon alkoxide is hydrolyzed in the presence of Si(OR)4, water, a catalyst, and an organic solvent. The amount of water used for hydrolysis is preferably between 0.8 and 5 equivalents relative to the alkoxy groups of Si(OR)4. If the amount of water is less than 0.8 equivalents, hydrolysis may not proceed sufficiently, and linear polysiloxane may not be obtained. If the amount of water is greater than 5 equivalents, the silicon alkoxide reaction described later may proceed randomly, forming a large amount of non-linear polysiloxane, and it may not be possible to obtain linear polysiloxane.

[0062] The catalyst used for hydrolysis is preferably an acid catalyst. Examples of acid catalysts include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and tartaric acid. Normally, the hydrolysis and polycondensation reactions of silicon alkoxides can proceed with either an acid catalyst or a base catalyst. However, when an acid catalyst is used, the monomers in the system are more easily hydrolyzed on average and tend to become linear. On the other hand, when a base catalyst is used, the reaction mechanism is such that the hydrolysis and polycondensation reactions of alkoxides bonded to the same molecule tend to proceed more easily, so the reaction proceeds randomly and the reaction product tends to have many voids. The amount of catalyst used is preferably 0.1 mol% to 0.5 mol% relative to the total molar amount of silicon alkoxide.

[0063] The organic solvent used for hydrolysis can be alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, or n-butyl alcohol, which are miscible with water and silicon alkoxide.

[0064] The hydrolysis temperature is preferably between 20°C and 45°C. If the reaction is carried out at a temperature below 20°C, the reactivity may be low, and the hydrolysis of Si(OR)4 may not proceed smoothly. On the other hand, if the reaction is carried out at a temperature above 45°C, the hydrolysis and polycondensation reactions proceed rapidly, which may result in gelation or the formation of a random, sparse polysiloxane that is not linear.

[0065] In the present invention, it is preferable that the total content of all water-soluble resins in the protective layer is 20 to 80% by mass of 100% by mass of the protective layer. When the water-soluble resin content is 20 to 80% by mass, the protective layer tends to have a dense structure, and excellent gas barrier properties tend to be exhibited along with the development of gas barrier properties. If the water-soluble resin content is less than 20% by mass, the protective layer tends to harden, and cracks may occur, which may reduce the gas barrier properties. If the water-soluble resin content is more than 80% by mass, the water-soluble resin may not be able to be immobilized, which may reduce the gas barrier properties. The water-soluble resin content is more preferably 30 to 60% by mass, and even more preferably 35 to 50% by mass. Furthermore, while the total content of all linear polysiloxanes in the protective layer may be 20 to 80% by mass of 100% by mass of the protective layer, as mentioned above, silicon alkoxides (including hydrolysates of silicon alkoxides) may also be included separately. Therefore, it is preferable that the total content of the inorganic components in the protective layer (hereinafter referred to as "protective layer inorganic components"), calculated by converting the linear polysiloxanes and silicon alkoxides to SiO2, is 20 to 80% by mass of 100% by mass of the protective layer. The content of the water-soluble resin and protective layer inorganic components in the protective layer can be measured by the method described later.

[0066] In the present invention, the mixing ratio of linear polysiloxane and silicon alkoxide in the protective layer can be adjusted. The mixing ratio is the mass ratio of linear polysiloxane and silicon alkoxide, calculated on an SiO2 basis, preferably in the range of linear polysiloxane / silicon alkoxide = 15 / 85 to 90 / 10, more preferably in the range of 50 / 50 to 85 / 15, and even more preferably in the range of 60 / 40 to 85 / 15. If this value exceeds 90 / 10, the interaction between linear polysiloxanes becomes stronger, making it impossible to immobilize the water-soluble resin, and the gas barrier properties may decrease. On the other hand, if it is less than 15 / 85, the number of Si-OH bonds derived from silicon alkoxide increases, which can increase hydrophilicity and decrease the gas barrier properties. The mixing ratio of linear polysiloxane and silicon alkoxide in the protective layer can be measured by the method described later.

[0067] Furthermore, by using an oligomer raw material with multiple Si(OR)4 groups already bonded as the linear polysiloxane, the mixing ratio of the linear polysiloxane and silicon alkoxide can be easily adjusted. Examples of oligomer raw materials with multiple Si(OR)4 groups already bonded include linear oligomers in which alkyl silicates such as methyl silicate (where R in chemical formula (1) is a methyl group) and ethyl silicate (where R is an ethyl group) are formed.

[0068] In this invention, a protective layer can be formed by promoting a polycondensation reaction between the linear polysiloxane and silicon alkoxide contained in the protective layer using heat. When the polycondensation reaction proceeds, the alkoxy groups and / or hydroxyl groups contained in the linear polysiloxane and silicon alkoxide decrease, resulting in a protective layer with a dense and tough structure. Furthermore, the polycondensation reaction increases the molecular weight of the linear polysiloxane and silicon alkoxide, thereby increasing its ability to fix vinyl resins. Therefore, since the gas barrier properties of the protective layer can be improved by promoting the reaction with heat, a higher temperature is preferable. However, if the temperature exceeds 200°C, the base film may shrink due to the heat, or strain and cracks may occur in the inorganic layer, reducing the gas barrier properties.

[0069] The protective layer can be obtained by coating an inorganic layer with a coating liquid containing the components of the protective layer (hereinafter abbreviated as "protective layer coating liquid") and drying it. Therefore, the drying temperature of the coating film, which is the temperature required to carry out the polycondensation reaction, is preferably 100°C to 200°C, more preferably 120°C to 180°C, and even more preferably 150°C to 180°C. If the temperature is below 100°C, the water contained as a solvent, as described later, may not evaporate sufficiently, and the layer may not harden.

[0070] The protective coating solution can be obtained by mixing a solution of a water-soluble resin dissolved in water or a water / alcohol mixed solvent with a solution containing a compound having a specific functional group, a linear polysiloxane, or a silicon alkoxide without a specific functional group. Examples of alcohols used as solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol.

[0071] The method for applying the protective coating liquid onto the inorganic layer is not particularly limited and any known method can be used, such as direct gravure, reverse gravure, microgravure, rod coat, bar coat, die coat, or spray coat.

[0072] The protective layer according to the present invention may contain leveling agents, crosslinking agents, curing agents, adhesion agents, stabilizers, ultraviolet absorbers, antistatic agents, etc., as long as the gas barrier properties are not impaired. Examples of crosslinking agents include silicon alkoxides such as aluminum, titanium, and zirconium, and their complexes.

[0073] The average thickness of the protective layer is preferably 10 nm to 1,000 nm, more preferably 100 nm to 600 nm, and even more preferably 350 nm to 500 nm. If the average thickness is less than 10 nm, it may not be able to adequately fill pinholes and cracks in the inorganic layer, and sufficient gas barrier properties may not be achieved. On the other hand, if the thickness exceeds 1,000 nm, cracks may occur due to the thickness.

[0074] As mentioned above, the protective layer undergoes a condensation reaction due to heat, improving its gas barrier properties. Therefore, it is preferable to further heat-treat the laminate after forming the protective layer to improve its gas barrier properties. The heat treatment temperature is preferably 30°C to 100°C, and more preferably 40°C to 80°C. The heat treatment time is preferably 1 day to 14 days, and more preferably 3 days to 7 days. If the heat treatment temperature is below 30°C, the thermal energy required to promote the reaction may be insufficient, resulting in a small effect. If it exceeds 100°C, curling or oligomerization of the substrate may occur, or the costs for equipment and manufacturing may increase.

[0075] [Analysis of protective layers] The presence of linear polysiloxane in the protective layer according to the present invention can be confirmed by laser Raman spectroscopy. In laser Raman spectroscopy, the Raman bands of linear polysiloxane and metal alkoxide (including hydrolysates of metal alkoxides) are 400-500 cm⁻¹, and the Raman bands of the 4-membered ring structure are 400-500 cm⁻¹. -1 These are observed at 495 cm². Because these Raman bands are superimposed, the four-membered ring structure is 495 cm². -1Linear polysiloxanes are 488 cm³. -1 Because the random network structure is not a single regular structure, 450cm -1 These are observed as bands with a certain extent, and the peaks can be separated by fitting them with a Gaussian function approximation.

[0076] This document describes a method for determining the content of water-soluble resin and inorganic components (linear polysiloxane and silicon alkoxide (including hydrolysates of silicon alkoxide)) in the protective layer. As mentioned above, the amount of inorganic components, such as linear polysiloxane and silicon alkoxide (including hydrolysates of silicon alkoxide), can be replaced by the amount of silicon, which can be obtained by X-ray fluorescence analysis. First, five standard samples with known silicon amounts and different silicon amounts are prepared, and X-ray fluorescence analysis is performed on each sample. X-ray fluorescence analysis generates element-specific fluorescent X-rays by X-ray irradiation and detects them. Since the amount of X-rays generated is proportional to the amount of the element contained in the sample being measured, the X-ray intensity S (unit: cps / μA) of silicon obtained by the measurement is proportional to the amount of silicon. Here, the thickness of the standard sample is calculated in the same way as the average thickness T described later, and the X-ray intensity S obtained by fluorescence X-ray analysis is divided by the thickness of the standard sample to calculate the X-ray intensity S per unit thickness. A calibration curve is then created by plotting the known silicon content against the X-ray intensity S per unit thickness. Subsequently, in the laminate of the present invention, the X-ray intensity S per unit thickness is similarly determined from fluorescence X-ray analysis and the average thickness T, and the silicon content is calculated from the calibration curve and its value. From this silicon content, the total number of moles of silicon atoms contained in the linear polysiloxane and silicon alkoxide is determined and converted to SiO2 mass, thereby determining the total mass ratio S of the protective layer inorganic components, and the content of the water-soluble resin and various inorganic components can be determined.

[0077] The mixing ratio of linear polysiloxane to silicon alkoxide in the inorganic components of the protective layer is determined by the laser Raman spectroscopy method, and the ratio A2 / A1, which is the ratio of the area A1 of the Raman band showing a random network structure to the area A2 of the Raman band showing linear polysiloxane, represents the mixing ratio of linear polysiloxane to silicon alkoxide (mass ratio in terms of SiO2).

[0078] [Packaging] The packaging of the present invention is formed by bonding the laminates of the present invention together using an adhesive component such as an adhesive to create a bag-like structure. The bonding surfaces may be the A layer or protective layer sides together, or one side may be the A layer or protective layer and the other side may be bonded to the base material. The packaging of the present invention has excellent gas barrier properties by using the laminates of the present invention. Therefore, defects such as gas degradation due to oxygen or water vapor do not occur after filling with contents, and the contents can be safely preserved. For example, it is possible to provide a packaging that does not deteriorate in gas barrier properties even when subjected to heat during boiling or retorting processes.

[0079] [Application] Because the laminate of the present invention has excellent gas barrier properties, it can be suitably used as packaging for food, pharmaceuticals, electronic components, and the like. [Examples]

[0080] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0081] [Evaluation Method] (1) Scanning transmission electron microscope (STEM) observation A microsampling system (FEI Helios G4) was used to prepare samples for cross-sectional observation using the FIB method. A scanning transmission electron microscope (JEOL JEM-ARM200F) was used to observe the cross-section of the sample at an acceleration voltage of 200kV, identify layer A of the laminate, and measure its thickness.

[0082] (2)XPS analysis Under the following conditions, compositional analysis was performed in the depth direction of layer A, and the film structure was confirmed by depth profiling. For metal elements, the oxide and metal components were separated and profiled. Data was collected from layer A through ion etching until it reached the substrate, and the presence or absence of a continuous increase or decrease in composition was confirmed from the obtained depth profiles of each element. A continuous increase or decrease was determined if the length of the increase or decrease was 2 nm or longer.

[0083] With respect to the thickness of layer A, the interface between layer A and the substrate side was defined as 0%, and the outermost surface as 100%. Analysis was performed at locations 5-25% in section X, 40-60% in section Y, and 75-95% in section Z. The average value of these regions was used as the analysis result, and the (O / Al) value for each location (section X, section Y, section Z) was calculated.

[0084] The measurement conditions were as follows: • Equipment: X-ray photoelectron spectrometer (Quantera SXM, manufactured by PHI Corporation) • Excitation X-ray: monochromatic AlKα 1,2 Line (1486.6eV) • X-ray diameter: 100 μm • Photoelectron escape angle: 45° (detector tilt relative to the sample surface) Ion etching conditions: Ar + Ion 3kV Raster size: 2 x 2 mm (etching area) Etching rate: 12.0 nm / min.

[0085] (3)EELS analysis The EELS analysis of the A layer was performed using an EELS detector (GATAN GIF Quantum). As specific measurement conditions, analysis was carried out at each location (X section, Y section, Z section) with an acceleration voltage of 200 kV, a beam diameter of 0.2 nm φ, and an energy resolution of 0.5 eV FWHM (full width at half maximum), and an absorption spectrum of the oxygen K edge was obtained. With respect to the thickness of the A layer, the interface with the base material side of the A layer was set to 0% and the outermost surface was set to 100%, and analysis was carried out at positions where the X section was 5 - 25%, the Y section was 40 - 60%, and the Z section was 75 - 95%, and the average value of the region was used as the analysis result.

[0086] After that, the peak intensities near 530 eV were denoted as I X (530), I Y (530), I Z (530), and the peak intensities near 540 eV were denoted as I X (540), I Y (540), I Z (540). From these, I X (530) / I X (540), I Y (530) / I Y (540), I Z (530) / I Z (540) was calculated.

[0087] (4) The presence or absence of hydrogen (H) in the A layer and the average composition of the A layer The average composition analysis of the A layer of the laminate was performed by the HR - RBS method (High Resolution Rutherford Backscattering Spectrometry) / HR - HFS method (High Resolution Hydrogen Forward scattering Spectrometry), and the ratio of aluminum (Al) atom concentration: oxygen (O) atom concentration: hydrogen (H) atom concentration was calculated. The detailed measurement conditions were as follows. <HR - RBS measurement> Apparatus: RBS analyzer HRBS500 manufactured by Kobe Steel, Ltd. Incident ion: He + Incident energy: 450 eV Incident angle: 60 deg Scattering angle: 60 deg Sample current: 30 nA Exposure: 12.5 μC <HR-HFS measurement> Apparatus: RBS analyzer HRBS500 manufactured by Kobe Steel, Ltd. Incident ion: N + Incident energy: 480 eV Incident angle: 70 deg Scattering angle: 30 deg Sample current: 2 nA Exposure: 0.4 μC (5) Component analysis and structure identification of the protective layer (water-soluble resin) The protective layer was peeled off from the sample and dissolved in a solvent that could be dissolved. Next, the solution was filtered to separate the particles and the filtrate. If necessary, general chromatography such as silica gel column chromatography, gel permeation chromatography, liquid high-speed chromatography, etc. was applied, and the components contained in the protective layer and the resin layer were separated and purified into single substances respectively. Then, DMSO-d6 was added to each single substance, heated to 60 °C and dissolved, and this solution was used as nuclear magnetic resonance spectroscopy, 1 1H-NMR, 13 13C-NMR measurements were performed. Next, for each single substance, IR method (infrared spectroscopy), various mass spectrometry methods (gas chromatography-mass spectrometry (GC-MS), pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS), matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), time-of-flight mass spectrometry (TOF-MS), time-of-flight matrix-assisted laser desorption ionization mass spectrometry (MALDI-TOF-MS), dynamic secondary ion mass spectrometry (Dynamic-SIMS), time-of-flight secondary ion mass spectrometry (TOF-SIMS)) were appropriately combined for qualitative analysis, and the components contained in the sample were identified and the structure was determined. In addition, when combining these qualitative analyses, those that could be measured with fewer combinations were preferentially applied.

[0088] (6) Measurement of the content ratio of water-soluble resin and inorganic components (linear polysiloxane, silicon alkoxide) in the protective layer. The mixture consisted of polyvinyl alcohol (hereinafter sometimes abbreviated as PVA; degree of polymerization 1,700, degree of saponification 98.5%) as a water-soluble resin and a hydrolyzed tetraalkoxysilane (hereinafter sometimes abbreviated as TEOS) as an inorganic component. Films obtained by mixing these materials in ratios of water-soluble resin to inorganic component (inorganic component calculated on a SiO2 mass basis) of 80 / 20, 65 / 35, 50 / 50, 35 / 65, and 20 / 80 were prepared as standard samples with different content ratios.

[0089] Next, the intensity of the specific silicon X-ray Kα was measured for each standard sample using a Shimadzu EDX-700 X-ray fluorescence analyzer, and the resulting X-ray intensity S (unit: cps / μA) was determined. The thickness of each standard sample was measured using the method described in (1) above, and the X-ray intensity S per unit thickness was calculated to create a calibration curve between the water-soluble resin and the inorganic component content (inorganic component is calculated on a SiO2 mass basis).

[0090] Next, for the laminate of the present invention, the X-ray intensity S per unit thickness was determined from the average thickness T using fluorescent X-ray analysis, and the content of water-soluble resin and inorganic components was determined from the calibration curve.

[0091] (7) Analysis of the silicon bonding state (presence or absence of linear polysiloxane), (mixing ratio of linear polysiloxane / silicon alkoxide (mass ratio in terms of SiO2)) The protective layer of the laminate was separated by cutting and analyzed by Raman spectroscopy under the following conditions. Measuring device: Jobin Yvon / Atago Bussan T-6400 Measurement mode: Micro-Raman Objective lens: 100x Beam diameter: 1 μm Light source:Ar + Laser / 514.5nm Laser power: 200mW Diffraction grating: Single 600gr / mm Slit: 100 μm Detector: CCD / Jobin Yvon, 1,024 x 256.

[0092] The following conditions were used to analyze the Raman spectra to calculate area A1 representing the random network structure of silicon alkoxides and area A2 representing the linear polysiloxane. The obtained Raman spectra were analyzed using the spectral analysis software GRAMS / Thermo Scientific. After baseline correction of the Raman spectra using linear approximation, the range was 600-250 cm⁻¹. -1 The fitting was performed within the specified range. The fitting was a 4-membered ring structure (peak wavenumber 495 cm²). -1 , half-width 35cm -1 ), linear polysiloxane (peak wavenumber 488 cm⁻¹) -1 , half-width 35cm -1 The random network structure, composed of silicon alkoxides, was separated into three components. Since the random network structure of silicon alkoxides exhibits a broad peak reflecting the continuous structure, it was automatically fitted by assuming separation into three components—the four-membered ring structure and the linear polysiloxane—using a Gaussian function approximation.

[0093] By calculating the area of ​​the region enclosed by the obtained bands and the baseline, the presence or absence of linear polysiloxane was determined. Additionally, the area representing the random network structure consisting of silicon alkoxides was designated as A1, and the area representing the linear polysiloxane as A2, and the mixing ratio of linear polysiloxane to silicon alkoxide (mass ratio in terms of SiO2) was calculated as A2 / A1.

[0094] (8) Oxygen barrier properties (oxygen permeability [cc / m³]) 2 / day]) The oxygen permeability of the laminate was measured in accordance with JIS K7126-2 (established August 20, 2006) using a MOCON OX-TRAN2 / 20 oxygen permeability analyzer under conditions of 23°C and 0% RH. Five samples taken from different locations were averaged to obtain the oxygen permeability [cc / m³]. 2 [ / day] was used.

[0095] (9) Water vapor barrier properties (water vapor transmission rate [g / m³]) 2 / day]) The water vapor transmission rate of the laminate was measured in accordance with JIS K7129B (established March 20, 2008) using a MOCON Permatran-W3 / 30 water vapor transmission rate analyzer under conditions of 40°C and 90% RH. Five samples taken from different locations were averaged, and the value was expressed as the water vapor transmission rate [g / m³]. 2 [ / day] was used.

[0096] (Example 1) (Formation of Layer A) Using the roll-up type vacuum deposition apparatus 3 shown in Figure 2, an aluminum oxide deposition layer was deposited as layer A with a target thickness of 8 nm by electron beam (EB) deposition. A polyethylene terephthalate film with a thickness of 12 μm (Toray Industries, Inc.'s "Lumirror" (registered trademark) P60) was used as the substrate.

[0097] The specific procedure is as follows: As the deposition material, granular aluminum (manufactured by Vacuum Metallurgy Co., Ltd., 99.99% purity) with a size of approximately 2-5 mm was set in the evaporation source 15. In the winding chamber 4, the unwinding roll 5 was set so that the side of the substrate 1 on which layer A is to be applied faced the evaporation source 15, and it was passed through the main drum 9 via unwinding rolls 6, 7, and 8. At this time, the temperature of the main drum was controlled to -30°C. Next, the pressure inside the vacuum deposition apparatus 3 was reduced using a vacuum pump, and 3.0 × 10⁻⁶ -3Pa was obtained. Next, an electron gun 17 was used as a heat source to melt the aluminum until it was no longer granular. Then, a linear anode layer type ion source 14 (Veeco, USA, ALS1000L), installed at a distance of 50 mm from the film running surface, was operated with 8 L / min of oxygen introduced, an anode voltage of 10 kV, and an anode current of 8.6 A to treat the substrate surface. The power supply for the ion source was a Glassman High Voltage SH type. Next, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction tubes 16a and 16b in a ratio of 1:9 (i.e., 1 L / min of oxygen gas was introduced from gas introduction tube 16a and 9 L / min from gas introduction tube 16b), and the input power, input current, and transport speed were adjusted so that the thickness of the A layer to be formed was targeted at 8 nm, and the A layer was formed on the surface of the substrate 1. As shown in Figure 4, a tubular shape was used as the oxygen gas introduction tube. The material was then wound onto the winding roll 13 via guide rolls 10, 11, and 12.

[0098] (Example 2) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction pipes 16a and 16c in a 1:1 ratio.

[0099] (Example 3) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, oxygen gas was introduced at a total rate of 10 L / min only from the oxygen gas introduction pipe 16a.

[0100] (Example 4) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction pipes 16a and 16b in a ratio of 0.5:9.5.

[0101] (Example 5) A laminate was obtained in the same manner as in Example 1, except that the A layer to be formed was deposited with a target thickness of 5 nm.

[0102] (Example 6) A laminate was obtained in the same manner as in Example 1, except that the A layer was deposited with a target thickness of 13 nm.

[0103] (Example 7) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, oxygen gas was introduced at a total rate of 10 L / min only from the oxygen gas introduction pipe 16b.

[0104] (Example 8) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction pipes 16b and 16c in a ratio of 9:1.

[0105] (Example 9) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, oxygen gas was introduced at a total rate of 10 L / min only from the oxygen gas introduction pipe 16c.

[0106] (Example 10) A laminate was obtained in the same manner as in Example 1, except that when forming layer A, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction pipes 16a, 16b, and 16c in a ratio of 1:8:1.

[0107] (Example 11) The laminate was obtained in the same manner as in Example 2, except that when forming layer A, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction pipes 16a and 16c in a ratio of 0.5:9.5.

[0108] (Example 12) The laminate was obtained in the same manner as in Example 2, except that when forming layer A, a total of 10 L / min of oxygen gas was introduced from oxygen gas introduction pipes 16a and 16c in a ratio of 9.5:0.5.

[0109] (Example 13) (Formation of Layer A) Using the roll-up type vacuum deposition apparatus 3 shown in Figure 2, an aluminum oxide deposition layer was deposited as layer A with a target thickness of 8 nm by resistance heating deposition method. A polyethylene terephthalate film with a thickness of 12 μm (Toray Industries, Inc.'s "Lumirror" (registered trademark) P60) was used as the substrate.

[0110] The specific procedure is as follows: Aluminum wire (manufactured by Nippon Light Metal Co., Ltd., 99.99% purity) was used as the deposition material, and a resistance heating boat was set as the evaporation source. In the winding chamber 4, the unwinding roll 5 was set so that the side of the substrate 1 on which layer A was to be applied faced the evaporation source 15, and the wire was passed through the main drum 9 via unwinding rolls 6, 7, and 8. At this time, the temperature of the main drum was controlled to -30°C. Next, the pressure inside the vacuum deposition apparatus 3 was reduced using a vacuum pump, and 8.0 × 10⁻⁶ -3 Pa was obtained. Next, aluminum wire was sent onto a resistance-heated boat and evaporated, and oxygen gas was flowed at a flow rate of 36 L / min to carry out deposition. The film speed was set to 6 m / s, and the supply speed of the aluminum wire was adjusted to achieve a target film thickness of 8 nm. Aluminum oxide film 1 m 2 The amount of oxygen gas per unit was 20 cc, and the relationship with the thickness of the deposited film [nm] was 2.5 cc / nm. A hollow cathode type plasma source was installed as a plasma generation unit diagonally above the deposition source, and argon gas was flowed through the hollow cathode type plasma source to excite the plasma by discharge. This plasma was drawn out directly above the boat by the opposing anode, and deposition was carried out while activating aluminum atoms and oxygen gas toward the film surface, forming layer A on the surface of substrate 1.

[0111] (Example 14) A laminate was obtained in the same manner as in Example 10, except that the following protective layer was laminated on layer A.

[0112] <Protective layer> As a water-soluble resin, polyvinyl alcohol (hereinafter abbreviated as PVA; degree of polymerization 1,700, degree of saponification 98.5%) was added to a solvent of water / isopropyl alcohol = 97 / 3 by mass ratio, and heated and stirred at 90°C to obtain a PVA solution with a solid content of 10% by mass.

[0113] Next, a hydrolysis solution of TEOS was obtained by adding 18.6 g of 0.02 N hydrochloric acid aqueous solution dropwise to a solution of 11.7 g of silicon alkoxide and 4.7 g of methanol while stirring.

[0114] Next, the PVA solution and the TEOS hydrolysis solution were mixed and stirred so that the solid content of PVA was 20% by mass, and then diluted with water to obtain a protective layer coating solution with a solid content of 13.4% by mass. This protective layer coating solution was applied to the inorganic layer by gravure coating and dried at 160°C to form a protective layer with an average thickness of 400 nm after drying.

[0115] (Example 15) A laminate was obtained in the same manner as in Example 10, except that the following protective layer was laminated on layer A.

[0116] <Protective layer> A PVA solution was obtained in the same manner as in Example 14.

[0117] Next, a solution of 11.7 g of TEOS, a silicon alkoxide, and 4.7 g of methanol was mixed, and 18.6 g of 0.02 N hydrochloric acid aqueous solution was added dropwise while stirring to obtain a TEOS hydrolysate. On the other hand, a solution of 11.2 g of ethyl silicate 48 (a linear oligomer with an average of 10 decamers) manufactured by Colcoat Co., Ltd., and 16.9 g of methanol was mixed, and 7.0 g of 0.06 N hydrochloric acid aqueous solution was added dropwise to obtain a decaper silicate hydrolysate. The decaper silicate hydrolysate and the TEOS hydrolysate were mixed so that the mass ratio of SiO2 equivalent solids was 80 / 20 to obtain a decaper silicate-TEOS hydrolysate mixture.

[0118] Next, the PVA solution and the aforementioned decaper silicate-TEOS hydrolysis mixture were mixed and stirred so that the solid content of PVA was 20% by mass, and then diluted with water to obtain a protective layer coating solution with a solid content of 13.4% by mass. This protective layer coating solution was applied to the inorganic layer by gravure coating and dried at 160°C to form a protective layer with an average thickness of 400 nm after drying.

[0119] (Example 16) Layer A was formed in the same manner as in Example 10.

[0120] Next, a laminate was obtained by forming a protective layer in the same manner as in Example 15, except that the water-soluble resin used for the protective layer was a modified polyvinyl alcohol containing a γ-butyrolactone structure having a carbonyl group in its cyclic structure.

[0121] Furthermore, the presence of a γ-butyrolactone structure in the modified polyvinyl alcohol of the protective layer was confirmed by the following method.

[0122] The protective layer is removed and heated to 60-80°C with DMSO-d6 to dissolve it. 1 H-NMR, 13 DEPT135 was measured using 1C-NMR. 1 From 1H-NMR, the signals appearing at 0.8 and 1.0 ppm were identified as peaks originating from methylene groups in the ring structure of γ-butyrolactone. The signal appearing at 2.3 ppm was identified as a peak originating from a methylene group adjacent to the carbonyl group in the ring structure of γ-butyrolactone. 13 From 1C-NMR, the signal appearing at 74 ppm was identified as a peak originating from the methylene group in the ring structure of γ-butyrolactone. The signal appearing at 174 ppm was identified as a peak originating from the carbonyl group in the ring structure of γ-butyrolactone. The signal appearing at 45 ppm was identified as a peak originating from the methylene group adjacent to the carbonyl group in the ring structure of γ-butyrolactone.

[0123] (Example 17) Layer A was formed in the same manner as in Example 10.

[0124] Next, a laminate was obtained by forming a protective layer in the same manner as in Example 16, except that the linear polysiloxane used for the protective layer was ethyl silicate 40 (a linear oligomer with an average of five molars) manufactured by Colcoat Co., Ltd.

[0125] (Comparative Example 1) A laminate was obtained in the same manner as in Example 1, except that oxygen gas was not introduced during the formation of layer A.

[0126] (Comparative Example 2) A laminate was obtained in the same manner as in Example 1, except that the total oxygen gas introduction rate for layer A was set to 3 L / min.

[0127] (Comparative Example 3) A laminate was obtained in the same manner as in Example 1, except that the total oxygen gas introduction rate for forming layer A was set to 20 L / min.

[0128] (Comparative Example 4) The laminate was obtained in the same manner as in Example 1, except that a pinhole-shaped oxygen gas introduction tube, as shown in Figure 3, was used when forming layer A.

[0129] Test specimens were cut from the laminates obtained in each example and comparative example, and various evaluations were performed. The results are shown in Tables 1 to 3.

[0130] [Table 1]

[0131] [Table 2]

[0132] [Table 3]

[0133] Examples 1-13 show that in layer A containing aluminum (Al) and oxygen (O), the film quality differs in one of the X, Y, or Z regions in the depth direction, and the average composition ratio of aluminum (Al) to oxygen (O) in the Z region (O / Al) was measured by X-ray photoelectron spectroscopy (XPS). Z (O / Al) Z The value must satisfy ≤2.00, and the average composition ratio (O / Al) in the Y section must be Y This is the ratio (O / Al). Y / (O / Al) Z However, (O / Al) Y / (O / Al) Z The result satisfied the condition ≤ 1.20.

[0134] In Examples 2 and 3, the oxidation degree of the Y portion of layer A was lower compared to Example 1 because the oxygen gas inlet tube 16b was not used, resulting in a larger I(530) / I(540) value for the Y portion than in Example 1. Also, in Examples 7-9, where the oxygen gas inlet tube 16a was not used when forming layer A, the (O / Al) value was higher compared to Example 1. Z The value was large. Furthermore, Example 13, in which a hollow cathode plasma source was used to highly activate the aluminum vapor and oxygen gas during deposition, showed particularly good gas barrier properties.

[0135] In Comparative Example 1, since layer A was formed without introducing oxygen, the oxygen (O) content ratio in the total atoms constituting layer A was 4.2 atm%, which is less than 5.0 atm%. Ta Unlike layer A of the present invention, this resulted in a layer of aluminum (Al) that does not contain oxygen (O).

[0136] In Comparative Example 2, the amount of introduced oxygen was extremely low compared to Example 1, resulting in a lower degree of oxidation, the formation of a layer A with a high concentration of aluminum oxide, and a film with significant variation in film quality. Similarly, in Comparative Example 3, the amount of introduced oxygen was extremely high compared to Example 1, resulting in the formation of a layer A with many defects and a film with significant variation in film quality.

[0137] Examples 14-17, which had a protective layer on the same A layer as in Example 10, showed further improved gas barrier properties. Of these, Example 15, in which linear polysiloxane was mixed with the metal alkoxide of the protective layer, showed improved gas barrier properties compared to Example 14, which did not contain linear polysiloxane. Example 16, in which the water-soluble resin was a modified polyvinyl alcohol containing a γ-butyrolactone structure with a carbonyl group in the cyclic structure, showed further improved gas barrier properties. In Example 17, in which the linear polysiloxane was changed to a linear oligomer with an average of five members, it was possible to adjust the gas barrier properties. [Industrial applicability]

[0138] The laminate of the present invention exhibits excellent gas barrier properties against oxygen gas, water vapor, etc., and is therefore suitable for use as a packaging material for food, pharmaceuticals, electronic components, etc., but its applications are not limited to these. [Explanation of symbols]

[0139] 1 Base material 2 A layer 3. Roll-type vacuum deposition apparatus 4. Winding Chamber 5. Unwinding Roll 6, 7, 8 Winding side guide roll 9 Main Drum 10, 11, 12 Winding side guide roll 13. Winding Roll 14 Ion Sources 15 Evaporation source 16a, 16b, 16c Oxygen gas inlet tube 17. Electron gun (EB gun) 19. Oxygen gas inlet tube 20 Gas inlet 21 Plasma generation section hollow cathode 22 Plasma 23 Anodes

Claims

1. A base film has a layer A on at least one side, and the layer A contains at least aluminum (Al) and oxygen (O). In the depth direction of the layer A, the area from 5.0% to 25.0% is defined as part X, the area from 25.0% to 75.0% as part Y, and the area from 75.0% to 95.0% as part Z, and these areas are defined as part X, part Y, and part Z, respectively. The average composition ratio of aluminum (Al) to oxygen (O) in part Z when measured by X-ray photoelectron spectroscopy (XPS) is (O / Al). Ｚ And the average composition ratio (O / Al) in section Y. Ｙ However, the laminate satisfies the following conditions (1) and (2). (1) 1.67≦(O / A) Ｚ ≦ 2.00 (2) 0.87≦(O / A) Ｙ / (O / Al) Ｚ ≦1.20

2. In the A layer, further containing hydrogen, the peak intensity near 530 eV of the oxygen K-edge spectrum of electron energy loss spectroscopy (EELS) analysis in each of the X part, Y part, and Z part is I Ｘ (530), I Ｙ (530), I Ｚ (530), the peak intensity near 540 eV of the oxygen K-edge spectrum of EELS analysis in each of the X part, Y part, and Z part in the A layer is I Ｘ (540), I Ｙ (540), I Ｚ (540), when I Ｙ (530) / I Ｙ (540) > I Ｘ (530) / I Ｘ (540) and / or I Ｙ (530) / I Ｙ (540) > I Ｚ (530) / I Ｚ (540), the laminate according to claim 1.

3. In the X and Z portions of the A layer, I Ｘ (530) / I Ｘ (540) ≤ 0.15 and / or I Ｚ (530) / I Ｚ The laminate according to either claim 1 or 2, wherein (540) ≤ 0.

25.

4. The laminate according to any one of claims 1 to 3, wherein the thickness of the A layer is 15.0 nm or less.

5. The laminate according to any one of claims 1 to 4, further comprising a protective layer on the A layer, wherein the protective layer further comprises a cured product containing a water-soluble resin and / or a metal alkoxide.

6. The laminate according to claim 5, characterized in that the protective layer further comprises a linear polysiloxane.

7. A method for manufacturing a laminate according to any one of claims 1 to 6, wherein a vapor-deposited layer is formed on at least one side of a substrate by evaporating aluminum by a vacuum deposition method and introducing oxygen into the aluminum vapor.

8. A method for manufacturing a laminate according to claim 7, wherein oxygen is introduced from the upstream and / or downstream side of the substrate.

9. A packaging body comprising the laminate according to any one of claims 1 to 6.

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