Laminate and method for manufacturing a laminate

Abstract

To provide a laminate that has high productivity and expresses gas barrier properties with reduced variations despite the thin film structure, and a method for producing a laminate.SOLUTION: A laminate has a substrate. At least one side of the substrate is provided with an A layer. The A layer at least includes aluminum (Al) and / or silicon (Si), and oxygen (O). For ESR analysis in the A layer, RA-RB≤6.0×1011( / cm2) holds where RA( / cm2) denotes a radical level before A layer etching and RB( / cm2) denotes a radical level after A layer etching.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate having excellent barrier properties against oxygen and water vapor, which can be suitably used as a packaging material for food, pharmaceuticals, electronic components, etc., and to a method for manufacturing the laminate. [Background technology]

[0002] Gas barrier films, which are formed by creating an inorganic compound film such as silicon dioxide or aluminum oxide on the surface of a film substrate using physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, or ion plating, or chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, or photochemical vapor deposition, are used to package various items such as food, pharmaceuticals, and industrial products that require the blocking of various gases such as water vapor and oxygen.

[0003] As methods to satisfy high gas barrier properties, methods have been proposed such as providing an undercoat layer between the substrate and the inorganic compound layer for the purpose of planarizing the substrate and improving adhesion (Patent Document 1), providing a planarizing layer between the substrate and the gas barrier layer, and further providing a planarizing layer formed by a sol-gel method using a composition containing other metal alkoxides and / or their hydrolysates laminated on the outer surface of the gas barrier layer (Patent Document 2), and forming multiple layers on the substrate and further providing a gas barrier coating layer on top thereof, which is formed by curing a polymerizable acrylic monomer or a mixture of monomer and oligomer (Patent Document 3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2000-043182 [Patent Document 2] Japanese Patent Publication No. 2005-324469 [Patent Document 3] Japanese Patent Publication No. 2008-036948 [Overview of the project] [Problems to be Solved by the Invention]

[0005] However, the method using the undercoat layer described in Patent Document 1 is superior in reducing defects in the inorganic compound layer and improving adhesion to the substrate surface by smoothing the substrate surface, but there is a problem in productivity due to an increase in the manufacturing process. Further, as described in Patent Documents 2 and 3, the method using a laminated structure is superior in less variation in barrier properties and mechanical properties, but there is also a problem in productivity due to an increase in the manufacturing process. Furthermore, an increase in the number of processes also becomes a factor in cost increase from the viewpoint of quality assurance in each process.

[0006] In view of the background of such prior art, an object of the present invention is to provide a laminate and a method for producing the laminate that have high productivity and exhibit gas barrier properties with little variation even in a thin film structure. [Means for Solving the Problems]

[0007] A preferred embodiment of the present invention is as follows. (1) Made of polyethylene terephthalate An A layer is provided on at least one side of a substrate, and the A layer contains at least aluminum (Al) and and oxygen (O), and in the electron spin resonance method (ESR) analysis in the A layer performed by the method described below, when the radical amount before A layer etching is R (per cm 2 ), and the radical amount after A layer etching is R B (per cm 2 ), then R A -R B ≦6.0×10 11 (per cm 2 ), a laminate. <Etching Method> Immerse the measurement sample in a 0.5% hydrofluoric acid aqueous solution until the A layer film thickness becomes 0.0%. The immersion time is determined after checking the etching rate for each sample. <ESR Analysis Method> [Narrow area] Measured temperature: Room temperature Central magnetic field: 3513 G Magnetic field sweep range: 150 G Modulation: 100 kHz, 4 G Microwave: 9.86 GHz, 0.1 mW Sweep time: 80 s × 32 times Time constant: 327.68 ms Number of points: 1000 points Cavity: Super-high-Q [Wide area] Measured temperature: Room temperature Central magnetic field: 3570 G Magnetic field sweep range: 200 G Modulation: 100 kHz, 5 G Microwave: 9.86 GHz, 0.1 mW Sweep time: 80 s × 32 times Time constant: 327.68 ms Number of points: 1000 points Cavity: Super-high-Q [ESR analysis method] For the radical amounts (per cm 2 ) before and after etching obtained by analysis, when the radical amount before etching with a g value of 2.0041 is R A (per cm 2 ) and the radical amount after etching is R (per cm B ), R 2 - R A (per cm B ) is determined 2 。 (2) In the depth direction in the A layer, when the positions of 5.0 to 25.0% of the length reference are defined as the X part, 40 .0 to 60.0% as the Y part, and 75.0 to 95.0% as the X part, Y part, and Z part respectively, the runs in each of the X part, Y part, and Z part are performed by the method described below ​Observation by transmission electron microscope - Oxygen K of electron energy loss spectroscopy (STEM-EELS) analysis The peak intensity near 530 eV of the edge spectrum is I X (530), I Y (530), I Z ( 530), the oxygen K of STEM-EELS analysis in each of the X part, Y part, and Z part in the A layer The peak intensity near 540 eV of the edge spectrum 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) is a (1) laminate described in <STEM Observation> Observation of the cross-section of the sample for observation by a scanning transmission electron microscope with an acceleration voltage of 200 kV is performed. <EELS Analysis> Acceleration voltage: 200 kV Beam diameter: 0.2 nm φ Energy resolution: 0.5 eV FWHM (full width at half maximum) (3) In the X part and Z part in the A layer, I X (530) / I X (540) ≤ 0.1 5 and / or I Z (530) / I Z (540) ≤ 0.25 (2) the laminate described in body. (4) The thickness of the A layer is 15.0 nm or less (1) to <​​​​(5) HR-RBS(High Resolution Rutherford Bac kscattering Spectrometry) / HR-HFS(High Re solution Hydrogen Forward scattering Spe When evaluated by the ctrometry method, the average composition of the A layer was determined to be aluminum (A l) Atomic concentration: Oxygen (O) atomic concentration: Hydrogen (H) atomic concentration is 15.0-40.0:40. 0~55.0:10.0~35.0 (atm%) (1)~ (4) Indicated in one of the following A laminate of [something]. (6) When evaluated using the HR-RBS / HR-HFS method, the average composition of the aforementioned A layer was determined to be AL The composition ratio of aluminum (Al) to oxygen (O) is O / Al = 1.20 to 2.20 (1) (5) A laminate as described in any of the following. (7) The aluminum is evaporated using a vacuum deposition method, and oxygen is introduced into the aluminum vapor. (1) ~ (6) The product described in any of the following A method for manufacturing layers. (8) Introduce oxygen from the upstream and / or downstream side of the substrate. (7) Manufacturing of the laminate described above method. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a laminate and a method for manufacturing a laminate that exhibits gas barrier properties with low variability even in a thin-film configuration and has high productivity. [Brief explanation of the drawing]

[0009] [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]

[0010] The details of the present invention are described below.

[0011] [Laminated structure] A preferred embodiment of the laminate of the present invention has a substrate having at least one side of a layer A, wherein the layer A comprises at least aluminum (Al) and / or silicon (Si), and oxygen (O), and in ESR analysis of the layer A, the amount of radicals in the layer A before etching is R A (pcs / cm 2 ), the amount of radicals after etching layer A, R B (pcs / cm 2 When R is set to ), A -R B ≤6.0 × 10 11 (pcs / cm 2 This is a laminated structure. The elements contained in layer A may include other elements as long as they contain at least aluminum (Al) and / or silicon (Si) and oxygen (O). For example, they may contain hydrogen (H), carbon (C), nitrogen (C), etc.

[0012] The statement that layer A contains aluminum (Al) means that, when evaluated using the HR-RBS (High Resolution Rutherford Backscattering Spectrometry) / HR-HFS (High Resolution Hydrogen Forward Scattering Spectrometry) method under the conditions described in the examples, the elemental content ratio of Al is 5.0 atm% or more out of 100.0 atm% of all atoms constituting layer A. The same applies to silicon (Si), oxygen (O), etc.

[0013] The HR-RBS / HR-HFS method is a technique that involves irradiating a target object with high-speed ions and obtaining the energy spectra of ions scattered behind Rutherford by atomic nuclei in the solid and hydrogen atoms scattered forward by elastic recoil, thereby obtaining the elemental composition of the object. Detailed evaluation conditions are as described in the examples.

[0014] In the ESR analysis of the A layer, the amount of radicals before etching the A layer is R A (pcs / cm 2 ), the amount of radicals after etching layer A, R B (pcs / cm 2 When R is set to ), A -R B ≤6.0 × 10 11 (pcs / cm 2 ) is preferable.

[0015] ESR analysis, or Electron Spin Resonance, is a spectroscopic analysis that observes the transitions between energy levels that occur when unpaired electrons are placed in a magnetic field. For example, in the case of a laminate with a two-layer structure consisting of layer A and a substrate, the amount of radicals before etching layer A is R A The results measured using the two-layer structure consisting of layer A and the substrate were used to determine the amount of radicals after etching layer A. B The results used are from measurements of a sample in which layer A has been removed by etching with hydrofluoric acid, as described later. The ESR analysis will be performed as follows.

[0016] <ESR Analysis Method> ESR analysis was performed using an electron spin resonance apparatus EMXplus (manufactured by Bruker). The sample was cut to about 12 mm × 90 mm, rolled into a measurement sample tube (quartz tube with an inner diameter of about 3 mm), and measured at room temperature. The analysis conditions were as described in the examples. When another layer was laminated on the A layer, the corresponding layer was removed before analysis. For example, when an organic coating layer was laminated, the coating layer was removed by dry etching such as RIE before measurement.

[0017] <Etching Method> The A layer is removed by hydrofluoric acid etching. The corresponding sample is immersed in a 0.5% hydrofluoric acid aqueous solution until the A layer film thickness becomes 0.0%. The immersion time is determined after confirming the etching rate for each sample.

[0018] <ESR Analysis Method> Regarding the radical amounts (number / cm 2 ) before and after etching obtained by analysis, when the radical amount before etching with a g value of 2.0041 is R A (number / cm 2 ) and the radical amount after etching is R B (number / cm 2 ), R A - R B (number / cm 2 ) is obtained.

[0019] The g value is a substance-specific value determined by the environment of the electron spin and can be obtained experimentally when the resonance frequency and the magnetic field strength are determined. The signal with a g value of 2.0041 is a signal caused by PET and can be used to estimate the radical amounts on the surface and inside of PET. Also, a signal may appear at a g value of 2.028, which is a signal derived from alumina. The radical amount R AThis parameter reflects the amount of radicals in layer A and the substrate, but since the signal with a g value of 2.0041 originating from layer A is hardly detected, it effectively reflects the amount of radicals on the PET surface near layer A, inside the PET, and on the PET surface further away from layer A. Since etching removes not only layer A but also the PET surface near layer A, the amount of radicals R after etching is also affected. B This reflects the amount of radicals inside the PET and on the PET surface furthest from layer A. In other words, R A -R B This corresponds to observing the amount of radicals near the PET surface, closer to layer A.

[0020] In ESR analysis of layer A, the amount of radicals before etching layer A is R A (pcs / cm 2 ), the amount of radicals after etching layer A, R B (pcs / cm 2 When R is set to ), A -R B ≤6.0 × 10 11 (pcs / cm 2 ) This means that the amount of radicals near the substrate surface closer to layer A is below a certain amount. The inventors of the present invention R A -R B ≤6.0 × 10 11 (pcs / cm 2 We found that by reducing the amount of radicals on the substrate surface that is in contact with layer A, the number of defects in layer A formed on top of it is reduced, resulting in a film with good barrier properties and less variability.

[0021] The fact that the amount of radicals on the substrate surface on the side contacting the A layer is large is considered to indicate that the elements of the A layer are not sufficiently bonded on the substrate surface on the side contacting the A layer. In that part, the degree of freedom of the molecular chains in the substrate becomes high, which is considered to prevent the A layer from becoming dense. Therefore, by reducing the amount of radicals on the substrate surface on the side contacting the A layer, it is considered that the A layer becomes dense, the defects are reduced, the barrier property is good, and the variation becomes less. Also, since the A layer is formed so as to accumulate from the part closer to the substrate in the A layer, if the part closer to the substrate in the A layer is in a dense state with few defects, it is considered that the entire A layer is also in a dense state with few defects. Further, since the fact that the amount of radicals is small is considered to indicate that the molecules on the substrate surface and the A layer are strongly bonded, it is considered that the A layer and the substrate are strongly adhered.

[0022] From the same viewpoint as above, R A -R B ≦4.5×10 11 (per cm 2 ) is more preferable, and R A -R B ≦3.0×10 11 (per cm 2 ) is even more preferable.

[0023] A preferred embodiment of the laminate of the present invention has an A layer on at least one side of a substrate, the A layer contains at least aluminum (Al) and / or silicon (Si), and oxygen (O), and regarding the amount of H (hydrogen atomic amount) in the D-SIMS analysis in the A layer, when the average value in the A layer is H ave. (atm / cm 3 ) and the maximum value in the A layer is H MAX (atm / cm 3 ), H MAX / H ave. =1.20 to 1.90, and the position where it becomes H MAX exists at a depth position of 40.0 to 65.0% from the outermost surface of the A layer, is a laminate.

[0024] D-SIMS analysis refers to Dynamic SIMS analysis, which is an analytical method for obtaining elemental distribution information in the depth direction by irradiating a sample with ions and mass-analyzing secondary ions sputter-released from the sample surface. For the D-SIMS analysis, a quadrupole type secondary ion mass spectrometer PHI ADEPT-1010 (manufactured by ULVAC-PHI, Inc.) is used and performed under the conditions described in the examples.

[0025] Regarding the amount of hydrogen (H), which is the amount of H in the D-SIMS analysis in layer A, the average value in layer A is H ave. (atm / cm 3 ) The maximum value in layer A is H MAX (atm / cm 3 ) When this is the case, H MAX / H ave. = 1.20 to 1.90, and it is preferable that the position where this occurs is at a depth position of 40.0 to 65.0% from the outermost surface of layer A. That H MAX / H MAX / H ave. = 1.20 to 1.90 means that hydrogen does not exist uniformly throughout, but rather there are locally places where the amount of hydrogen is large in the thickness direction. In such places where the amount of hydrogen is large, many exist as AlOOH, and AlOOH functions to trap permeating moisture by hydrogen bonding. On the other hand, where there is a large amount of AlOOH, the denseness of the film decreases. Therefore, it is considered that when H MAX / H ave. = 1.20 to 1.90, the barrier property becomes good.

[0026] H MAX The fact that the position where this occurs is at a depth position of 40.0 to 65.0% from the outermost surface of layer A means that the location where the AlOOH abundance is high exists near the center in the depth direction of layer A. Since the amount of moisture that can be trapped by AlOOH is limited, at depth positions of 0.0 to 39.9% and 65.1 to 100.0% in the depth direction of layer A, the film density is increased to shield moisture as much as possible, and at a depth position of 40.0 to 65.0%, it is considered that by trapping the permeating moisture, an excellent barrier property is exhibited as a whole.

[0027] In other words, by adopting the above configuration, the permeate gas can be blocked by two mechanisms: the density of the film and trapping by AlOOH, etc., resulting in good barrier properties and less variability.

[0028] From the same perspective as above, H MAX / H ave. =1.40~1.90 and H MAX It is more preferable that the position where this occurs is located at a depth of 50.0 to 60.0% from the outermost surface of layer A. Even more preferable is H MAX / H ave. = 1.50 to 1.80.

[0029] D-SIMS analysis showed H ave. and H MAX In calculating this, layer A is defined as follows: The interface between layer A and the substrate is defined as (C1+C2) / 2, where C1 is the average carbon content of the substrate and C2 is the average carbon content of layer A, as determined by D-SIMS analysis. The region from the reference interface to the surface is defined as the layer A region in D-SIMS. The method for converging the average carbon content values ​​and the approach for including layers other than layer A and the substrate are the same as those used in the HR-RBS / HR-HFS method described later. The average value of H in layer A in D-SIMS analysis is H ave. This value is the average of the measurement results in the range of 15.0% to 70.0% from the surface of layer A. Also, the maximum value of H in layer A is given. MAX The maximum value is defined as the maximum measurement result in the range of 15.0% to 70.0% from the surface of layer A. MAX The location of the maximum value is calculated by dividing the thickness from the surface of layer A to the location of the maximum value by the thickness of layer A. The reason for excluding 0.0-14.9% and 70.1-100.0% from the surface of layer A is that these areas are prone to noise due to surface contamination and interfacial mixing. Furthermore, the reason for excluding a wider area on the interface side is that the range of mixing tends to vary depending on the contained elements.

[0030] The following methods are preferred as means to achieve the above-described laminate. It is preferable to appropriately adjust the position, amount, and method of introducing oxygen gas. Specifically, taking the roll-up 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 -3 When aluminum is evaporated at 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 layer A of 8 nm, 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 unidirectional 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. By blowing oxygen locally to the targeted location as described above, it becomes easier to efficiently bond with the carbon on the substrate surface to form covalent bonds and then Al-O bonds. As the carbon on the substrate surface bonds efficiently, the amount of radicals on the substrate surface is reduced. Furthermore, by blowing oxygen locally at a targeted location, the degree of oxidation can be increased near the surface and / or interface of layer A, while the degree of oxidation can be decreased near the center of layer A in the depth direction, allowing AlOOH to be formed and increasing the amount of H. In other words, by blowing oxygen locally at a targeted location, H MAX At a depth of 40.0-65.0% from the outermost surface of layer A, H MAX / H ave. It can be set to 1.20 to 1.90.

[0031] 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), IZ (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.

[0032] 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. The peak intensity around 530 eV, denoted as I(530), 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.

[0033] EELS analysis is performed using STEM-EELS (Scanning Transmission Electron Microscopy-Electron Energy Loss Spectroscopy). For sample pretreatment before STEM-EELS measurement, the FIB (Focused Ion Beam) method is used. Specifically, samples for cross-sectional observation are prepared using a microsampling system based on the method described in "Polymer Surface Processing" (by Akira Iwamori), pp. 118-119. During this process, all samples are handled in a glove box (under a nitrogen atmosphere), except when carbon deposition is performed to impart conductivity to the surface. Detailed measurement conditions are as described in the examples. The approximate locations of the aluminum (Al) and oxygen (O) layers are determined using the aforementioned HR-RBS / HR-RFS method. The interfaces of these layers are then determined using STEM measurement. EELS measurements are performed on the X, Y, and Z regions of these layers to determine I(530) and I(540) for each region.

[0034] When performing EELS measurements, 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 40.0-60.0% of the A layer thickness. Furthermore, the Z region refers to the area at 75.0-95.0% of the said thickness. The A layer thickness is measured from cross-sectional observation images obtained by STEM (scanning transmission electron microscope). 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.

[0035] When there are multiple layers containing aluminum (Al) and oxygen (O), in at least one layer, Y (530) / I Y(540)>I X (530) / I X (540) and / or I Y (530) / I Y (540)>I Z (530) / I Z If (540), the laminate has an A layer, the A layer contains at least aluminum (Al) and oxygen (O), and 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)

[0036] 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.

[0037] I Y (530) / I Y (540)>I X (530) / I X (540) and / or I Y (530) / I Y (540)>I Z (530) / IZ (540) indicates that the amount of hydroxide in the outer portion (X and / or Z) is less than that of Y. The lower amount of hydroxide in the outer portion (X and / or Z) compared to Y results in higher density in the outer portion (X and / or Z), preventing moisture from entering the A layer from the outside. In other words, preventing moisture from entering the A layer from the outside minimizes changes in the A layer's film quality, thus reducing variations in film quality. As a result, variations in water vapor permeability can be further reduced. From the viewpoint of the above-mentioned variations in film quality and barrier properties, 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) / I Z (540) is even more preferable.

[0038] 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 tube with an introduction direction in one direction as shown in Figure 4, and introducing a large amount of oxygen upstream of the substrate and / or 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 directly above the evaporation source, 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.

[0039] 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. The inclusion of hydrogen (H) can impart flexibility to the laminate.

[0040] 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 barrier properties. From the viewpoint of 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.

[0041] 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.

[0042] 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).

[0043] Let X be the thickness of layer A (nm), and Y be the water vapor transmission rate (g / m³). 2 When X × Y is set to ( / day), it is preferable that X × Y ≤ 20.0. Having X × Y ≤ 20.0 allows even thin films to exhibit barrier properties. From the viewpoint of productivity and cost, X × Y ≤ 15.0 is more preferable, and X × Y ≤ 8.0 is even more preferable. Water vapor transmission can be measured using a water vapor transmission meter in a 40°C 90%RH environment. Note that in the above measurement unit, "day" corresponds to 24 hours.

[0044] The laminate of the present invention is preferably a laminate in which, when the HR-RBS / HR-HFS method is used and the locations at 5.0-25.0%, 40.0-60.0%, and 75.0-95.0% of the length in the depth direction of layer A are defined as sections X, Y, and Z, respectively, there are sections in which the composition ratio of aluminum (Al) to oxygen (O) is different (O / Al).

[0045] The HR-RBS / HR-HFS method allows us to obtain a graph of the composition ratio in the depth direction. 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 region for layer A in the HR-RBS / HR-HFS method. Unless otherwise specified, the average composition of layer A is calculated by averaging the measurement results at each measurement point in this measurement region. 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 calculated 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.

[0046] When measuring using the HR-RBS / HR-HFS 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 the inorganic compound layer (layer A) identified by the HR-RBS / HR-HFS method, based on length. The Y region refers to the area at 40.0-60.0% 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. Furthermore, the composition of each part shall be calculated by averaging the measurement results at each measurement point in each part.

[0047] The presence of areas with different aluminum (Al) to oxygen (O) composition ratios (O / Al) means that any of the O / Al values ​​for the X, Y, and Z sections defined above, as measured by the HR-RBS / HR-HFS method, differ by 0.10 or more. On the other hand, if areas with different O / Al composition ratios exist, it is preferable that the difference is 0.50 or less, as this reduces the number of areas with high concentrations of aluminum peroxide or aluminum monoxide relative to the average composition of layer A, resulting in a film with good barrier properties and less variability.

[0048] The presence of varying O / Al composition ratios in the depth direction within layer A allows for the coexistence of dense and relatively sparse, highly flexible areas within the same film. If the entire layer A were dense throughout its depth, it would be a rigid film prone to cracking and in-plane variation. On the other hand, by coexisting dense and highly flexible areas within the same film in the depth direction, it is possible to achieve a film that is less prone to cracking, has good barrier properties, and exhibits less in-plane variation.

[0049] From the same perspective, it is preferable that any one of the values of the X part, the Y part, and the Z part has a difference of 0.15 or more. Further, as the part with a difference, it is preferable that there is a difference of 0.10 or more between the X part and the Y part, and / or there is a difference of 0.10 or more between the Z part and the Y part. The specific measurement conditions for the element ratio of Al and O in the A layer are as described in the examples. When there are multiple layers containing aluminum (Al) and oxygen (O), if there are locations where the composition ratio O / Al is different in the depth direction in at least one layer, it has an A layer, the A layer contains at least aluminum (Al) and oxygen (O), and when the locations of 5.0 to 25.0% of the length standard, 40.0 to 60.0% of the locations, and 75.0 to 95.0% of the locations in the depth direction in the A layer are defined as the X part, the Y part, and the Z part respectively, it is assumed to be a laminate in which there are locations where the composition ratio O / Al of aluminum (Al) and oxygen (O) is different. Here, one layer refers to a part that has a distinguishable boundary surface with an adjacent part in the thickness direction and has a finite thickness. More specifically, when observing the cross-section of the A layer with a scanning transmission electron microscope (STEM) as described in the examples, it refers to what is distinguished by a discontinuous boundary surface. Even if the composition changes in the thickness direction of the A layer, if there is no such boundary surface between them, it is treated as one layer.

[0050] Also, particularly from the perspective of reducing the variation in barrier properties, for the composition ratio O / Al, it is preferable that the composition ratio O / Al of the X part ≠ the composition ratio O / Al of the Y part and / or the composition ratio O / Al of the Y part ≠ the composition ratio O / Al of the Z part. From the same perspective, for the composition ratio O / Al, it is more preferable that the composition ratio O / Al of the X part > the composition ratio O / Al of the Y part and / or the composition ratio O / Al of the Y part < the composition ratio O / Al of the Z part.

[0051] Regarding the average composition of layer A, it is preferable that the composition ratio of aluminum (Al) to oxygen (O) is 1.20 ≤ O / Al ≤ 2.20. A ratio of 1.20 ≤ O / Al ≤ 2.20 results in a higher proportion of aluminum existing as aluminum oxide or aluminum hydroxide rather than metallic aluminum in layer A, thus improving transparency and barrier properties. From the viewpoint of transparency and barrier properties, a ratio of 1.40 ≤ O / Al ≤ 2.10 is more preferable. The elemental ratio of Al to O in layer A shall be measured by the HR-RBS / HR-HFS method. The specific measurement conditions are as described in the examples. Furthermore, even if O / Al = 1.5, the aluminum is not necessarily a complete oxide; it may contain hydroxide, aluminum monoxide, or aluminum peroxide. This is because, even if moisture in the atmosphere during deposition and moisture adhesion after deposition are prevented, residual moisture in the deposition tank and moisture contained in the substrate are incorporated into the film during and after deposition.

[0052] 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.

[0053] [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.

[0054] 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.

[0055] 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.

[0056] 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.-2 A vacuum level of Pa or less is preferable. The ultimate vacuum level is 5.0 × 10⁻⁶. -3 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.

[0057] [Base material] The substrate used in the present invention is preferably in the form of a film from the viewpoint of ensuring flexibility. The film may be a single-layer film or a film of two or more layers, for example, a film produced by co-extrusion. The type of film may be an unoriented, uniaxially oriented, or biaxially oriented film.

[0058] The material of the base material used in the present invention is not particularly limited, but it is preferable that it mainly consists of an organic polymer. Examples of organic polymers that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymers, polyacrylonitrile, polyacetal, and various other polymers. Among these, polyethylene terephthalate and polypropylene, which have excellent transparency and versatility, are preferred. Furthermore, the organic polymer may be a homopolymer or a copolymer, and only one type of organic polymer may be used, or multiple types may be blended and used.

[0059] The surface of the substrate on which layer A is formed may be pre-treated to improve adhesion and smoothness, such as corona treatment, plasma treatment, ultraviolet treatment, ion bombardment 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 substrate from 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 and to increase the scratch resistance of the substrate.

[0060] The thickness of the substrate used in the present invention is not particularly limited, but from the viewpoint of ensuring flexibility, it is preferably 200 μm or less, and from the viewpoint of ensuring strength against tensile and impact, it is preferably 5 μm or more. Furthermore, from the viewpoint of ease of processing and handling of the film, the thickness of the substrate is preferably 10 μm or more, and from the viewpoint of use as a packaging material, it is more preferably 25 μm or less.

[0061] [Other layers] On the outermost surface of the laminate of the present invention, that is, on layer A, an overcoat layer may be formed to improve scratch resistance, printability, retort resistance, etc., to the extent that gas barrier properties are not reduced, or a laminated structure may be formed by laminating an adhesive layer or film made of an organic polymer compound for bonding. The outermost surface referred to here is the surface of layer A after it has been laminated onto the substrate.

[0062] [Applications of laminates] The laminate of the present invention has excellent barrier properties against oxygen and water vapor, exhibits low variability, and is low-cost, making it suitable for use as a gas barrier film. The laminate of the present invention can be suitably used as a packaging material for food, pharmaceuticals, electronic components, and the like. [Examples]

[0063] The present invention will be described in detail below based on examples. However, the present invention is not limited to the following examples.

[0064] [Evaluation Method] (1)ESR analysis ESR analysis was performed using an electron spin resonance spectrometer (EMXplus, manufactured by Bruker). The sample was cut to approximately 12 mm x 90 mm, rolled up and placed in an ESR measurement sample tube (quartz tube with an inner diameter of approximately 3 mmφ), and measured at room temperature. The specific measurement conditions used were as follows: Observed R A (pcs / cm 2 ), R B (pcs / cm 2 The g-value used was 2.004. [Narrow area] Measurement temperature: room temperature Center magnetic field: 3513G Magnetic field sweep range: 150G Modulation: 100kHz, 4G Microwave: 9.86GHz, 0.1mW Sweeping time: 80s x 32 times Time constant: 327.68 ms Points: 1000 points Cavity: Super-high-Q [Wide area] Measurement temperature: room temperature Center magnetic field: 3570G Magnetic field sweep range: 200G Modulation: 100kHz, 5G Microwave: 9.86GHz, 0.1mW Sweeping time: 80s x 32 times Time constant: 327.68 ms Points: 1000 points Cavity: Super-high-Q (2)D-SIMS analysis D-SIMS analysis was performed using a quadrupole secondary ion mass spectrometer PHI ADEPT-1010 (ULVAC-PHI). Data was collected at 0.1 nm depth intervals. The specific measurement conditions used were as follows: Attention element H Primary ion species Cs + Primary ion acceleration energy: 1 keV Secondary ion polarity Negative Oxygen leak No. E-gun charge compensation (3) 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.

[0065] (4)EELS analysis The EELS analysis of the A layer was carried out using an EELS detector (GATAN GIF Quantum). As specific measurement conditions, analysis was performed 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 at 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 5.0 to 25.0%, the Y section was 40.0 to 60.0%, and the Z section was 75.0 to 95.0%, and the average value of the region was used as the analysis result.

[0066] Subsequently, the peak intensities around 530 eV were designated as I X (530), I Y (530), I Z (530), and the peak intensities around 540 eV were designated 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.

[0067] (5) Composition of the A layer The composition analysis of the A layer of the laminate was carried out by the HR - RBS / HR - HFS method. 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 Irradiation dose: 12.5 μC <HR - HFS measurement> Apparatus: RBS analyzer HRBS500 manufactured by Kobe Steel, Ltd. Incident ion: N + Incident energy: 480 eV Incident angle: 70deg Scattering angle: 30deg Sample current: 2nA Irradiation dose: 0.4μC (6) 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 at 23°C and 0% RH. Five samples taken from different locations were averaged to determine the oxygen permeability (cc / m³). 2 The calculation was performed using the formula ( / day). Additionally, the standard deviation of 5 points was calculated to represent the variability.

[0068] (7) 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 this value was expressed as the water vapor transmission rate (g / m³). 2 The calculation was performed using the formula ( / day). Additionally, the standard deviation of 5 points was calculated to represent the variability.

[0069] (8) Total light transmittance The total light transmittance of the laminate was measured using a NDH4000 haze meter manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS K7361 (established in 1997). Two measurements were taken, the obtained data were averaged, and the result was rounded to two decimal places to obtain the average value at that level, which was then defined as the total light transmittance (%).

[0070] (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.

[0071] 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 -3 Pa was obtained. Next, an electron gun 17 was used as a heating 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 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.

[0072] (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.

[0073] (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.

[0074] (Example 4) 8.0 × 10 inside the vacuum chamber -3 A laminate was obtained in the same manner as in Example 1, except that the pressure was reduced to Pa to form layer A.

[0075] (Example 5) 3.0 × 10 inside the vacuum chamber -2 A laminate was obtained in the same manner as in Example 1, except that the pressure was reduced to Pa to form layer A.

[0076] (Example 6) 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 1:4.

[0077] (Example 7) 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.

[0078] (Example 8) 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.

[0079] (Example 9) 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 13 nm.

[0080] (Example 10) 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.

[0081] (Example 11) 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.

[0082] (Example 12) 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 through the oxygen gas introduction pipe 16c.

[0083] (Example 13) 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.

[0084] (Example 14) 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.

[0085] (Example 15) 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.

[0086] (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.

[0087] (Comparative Example 2) A laminate was obtained in the same manner as in Example 1, except that the total oxygen gas introduction rate was set to 1 L / min when forming layer A.

[0088] (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.

[0089] (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.

[0090] Test specimens were cut from the laminates obtained in each example and comparative example, and various evaluations were performed. The results are shown in Table 1.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] [Table 4] [Industrial applicability]

[0095] 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]

[0096] 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

Claims

1. A substrate made of polyethylene terephthalate has a layer A on at least one side, the layer A contains at least aluminum (Al) and oxygen (O), and in electron spin resonance (ESR) analysis of the layer A performed by the method described below, the amount of radicals before etching of the layer A is R Ａ (pcs / cm ２ ), the amount of radicals after etching the A layer R Ｂ (pcs / cm ２ When R is set to ), Ａ -R Ｂ ≤ 6.0 × 10 １１ (pcs / cm ２ A laminated structure, which is a laminate. <Etching Method> The sample to be measured is immersed in a 0.5% hydrofluoric acid aqueous solution until the thickness of layer A reaches 0.0%. The immersion time is determined after checking the etching rate for each sample. <ESR analysis method> [Narrow area] Measurement temperature: room temperature Center magnetic field: 3513G Magnetic field sweep range: 150G Modulation: 100 kHz, 4G Microwave: 9.86 GHz, 0.1 mW Sweeping time: 80 s x 32 times Time constant: 327.68 ms Points: 1000 points Cavity: Super-high-Q [Wide Area] Measurement temperature: room temperature Center magnetic field: 3570G Magnetic field sweep range: 200G Modulation: 100 kHz, 5G Microwave: 9.86 GHz, 0.1 mW Sweeping time: 80 s x 32 times Time constant: 327.68 ms Points: 1000 points Cavity: Super-high-Q <ESR analysis method> The radical amounts before and after etching obtained by the analysis (number / cm ２ ), for the radical amount before etching with a g-value of 2.0041, let it be R Ａ (number / cm ２ ), and for the radical amount after etching, let it be R Ｂ (number / cm ２ ). When this is the case, calculate R Ａ - R Ｂ (number / cm ２ ).

2. In the depth direction of the aforementioned layer A, when the area from 5.0% to 25.0% of the length is defined as section X, the area from 40.0% to 60.0% as section Y, and the area from 75.0% to 95.0% as sections X, Y, and Z, respectively, the peak intensity around 530 eV of the oxygen K-edge spectrum obtained by scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) analysis in each of the sections X, Y, and Z, performed by the method described below, is defined as I Ｘ (530), I Ｙ (530), I Ｚ (530) The peak intensity around 540 eV of the oxygen K-edge spectrum of the STEM-EELS analysis in the X, Y, and Z regions of the A layer 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 The laminate according to claim 1, which is (540). <STEM observation> Using a scanning transmission electron microscope, the cross-section of the sample is observed with an accelerating voltage of 200 kV. <EELS analysis> Acceleration voltage: 200kV Beam diameter: 0.2 nmφ Energy resolution: 0.5 eV FWHM (full width at half maximum)

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 claim 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. A laminate according to any one of claims 1 to 4, wherein, when evaluated by the HR-RBS (High Resolution Rutherford Backscattering Spectrometry) / HR-HFS (High Resolution Hydrogen Forward scattering Spectrometry) method, the average composition of the A layer is such that the aluminum (Al) atom concentration: oxygen (O) atom concentration: hydrogen (H) atom concentration is 15.0 to 40.0: 40.0 to 55.0: 10.0 to 35.0 (atm%).

6. The laminate according to any one of claims 1 to 5, wherein, when evaluated by the HR-RBS / HR-HFS method, the average composition of the A layer has a composition ratio of aluminum (Al) to oxygen (O) of O / Al = 1.20 to 2.

20.

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 vacuum deposition 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.

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