Laminate, method for manufacturing laminate, flexible device, solar cell and optical sensor

Abstract

To provide a laminate having high gas barrier properties and high flexibility even in a simple structure.SOLUTION: A laminate includes an A layer on at least one side of a base material and a B layer between the base material and the A layer. The A layer includes at least two kinds of metal elements selected from a group consisting of Mg, Si, Zn, Ti, Al, Ce, Sc, Sr and oxygen; the B layer has a thickness of less than 10 nm; and thickness of the B layer is 10% or less of that of the A layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate used as a packaging material for foods and pharmaceuticals that require high gas barrier properties, and as a material for electronic components such as solar cells, electronic paper, and organic electroluminescence (EL) displays, as well as to a flexible device, a solar cell, an optical sensor, and a method for producing the laminate. [Background technology]

[0002] Gas barrier films, which are formed by forming thin films of inorganic or organic materials on the surface of a film substrate using physical vapor deposition (PVD) methods such as vacuum deposition and sputtering, or chemical vapor deposition (CVD), are used as packaging materials for foods and pharmaceuticals that require the blocking of various gases such as water vapor and oxygen, as well as electronic device components such as electronic paper and solar cells. -3 g / m 2 High gas barrier properties of less than 1 / day are required.

[0003] As a method for obtaining high gas barrier properties, a gas barrier film has been proposed in which organic and inorganic layers are alternately laminated in multiple layers, thereby preventing the occurrence of defects through a hole-filling effect (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-324406 Summary of the Invention [Problem to be solved by the invention]

[0005] As in Patent Document 1, it is possible to achieve high barrier properties by alternately laminating organic and inorganic layers in multiple layers, but this can result in a lack of flexibility due to the difference in elasticity between the organic and inorganic layers, and the number of steps required for laminating multiple layers is increased.

[0006] In view of the background of the prior art, the present invention aims to provide a laminate that has a high level of gas barrier property and high flexibility even with a simple structure. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention employs the following means. That is, a preferred embodiment of the present invention is as follows. (1) A laminate having an A layer on at least one side of a substrate and a B layer between the substrate and the A layer, wherein the A layer contains at least two metal elements selected from the group consisting of Mg, Si, Zn, Ti, Al, Ce, Sc, and Sr, and oxygen, and the B layer contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, and oxygen, and the thickness of the B layer is less than 10 nm and is 10% or less of the thickness of the A layer. (2) The laminate according to (1), wherein the element ratio of oxygen in the layer B is 50 to 80 atm % when the composition is evaluated by X-ray photoelectron spectroscopy. (3) The laminate according to (1) or (2), wherein the mean annihilation lifetime of positrons measured from the layer A side by a positron beam method is 0.750 ns or less. (4) The laminate according to any one of (1) to (3), wherein the degree of oxidation in the average composition of the layer A, represented by the following formula, is 0.9 to 1.7:

[0008] Formula Oxidation degree=X / ((b1 / a1)×Y1+(b2 / a2)×Y2+...) When the average composition in Layer A is evaluated using X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by analysis is designated X, and the element ratios of metal elements M1, M2... are designated Y1, Y2.... When the composition ratio of the most stable oxide of each metal element in the atmosphere is M:O = a:b, the degree of oxidation in the average composition of Layer A is calculated as X / ((b1 / a1) × Y1 + (b2 / a2) × Y2 +...). The peaks used in the analysis are 1s for magnesium, 2p for silicon, 1s for oxygen, 2p for aluminum, 2p for zinc, 2p for calcium, 3d for zirconium, 2p for titanium, 3d for cerium, 2p for scandium, and 3d for strontium. (5) The laminate according to any one of (1) to (4), wherein the degree of oxidation in the average composition of the interface portion of the layer A, represented by the following formula, is 0.9 to 1.7.

[0009] Formula Oxidation degree=X / ((b1 / a1)×Y1+(b2 / a2)×Y2+...) When the average composition of the interface of Layer A is evaluated using X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by analysis is designated X, and the element ratios of metal elements M1, M2... are designated Y1, Y2.... When the composition ratio of the most stable oxide of each metal element in the atmosphere is M:O = a:b, the degree of oxidation in the average composition of the interface of Layer A is calculated as X / ((b1 / a1) × Y1 + (b2 / a2) × Y2 +...). The peaks used in the analysis are 1s for magnesium, 2p for silicon, 1s for oxygen, 2p for aluminum, 2p for zinc, 2p for calcium, 3d for zirconium, 2p for titanium, 3d for cerium, 2p for scandium, and 3d for strontium.

[0010] The interface of layer A is determined by depth direction analysis using X-ray photoelectron spectroscopy (XPS), and when layers A and B are composed of different metal elements, the average metal element amount M A In contrast to M A The depth at which the oxygen concentration in the A layer is 1 / 2 is the interface between the A layer and the B layer, and the range is from the interface between the A layer and the B layer to 6 nm toward the surface of the A layer. In addition, when the A layer and the B layer are composed of the same metal element, the average oxygen content in the A layer is M AO and the oxygen content of layer B, M BO When the amount of oxygen is (M AO +M BO ) / 2 is the interface between the A layer and the B layer, and the range is from the interface between the A layer and the B layer to 6 nm toward the surface of the A layer. (6) The laminate according to any one of (1) to (5), wherein the layer A contains at least one element selected from the group consisting of Al, Mg, Zn, and Ca, and Si. (7) The laminate according to (6), wherein the layer A contains Mg and Si, and has an Mg element ratio of 5 to 50 atm%, an Si element ratio of 2 to 40 atm%, and an O element ratio of 45 to 75 atm%, as measured by X-ray photoelectron spectroscopy. (8) The A layer has an average composition (atm%) of Mg atoms and Si atoms of the A layer of YA Mg and YA Si When the ratio of Mg atoms to the sum of Si atoms and Mg atoms is YA Mg / (YA Mg +YA Si ) is 0.30 to 0.80. (9) The laminate according to any one of (1) to (8), wherein the layer B contains at least one element selected from the group consisting of Al, Mg, Zn, In, Sn, and Si. (10) The B layer contains Mg and Si, and the element ratio (atm%) of Mg atoms to Si atoms in the B layer is YB Mg and Y.B. Si When the ratio of Mg atoms to the sum of Si atoms and Mg atoms is YB Mg / (YB Mg +YB Si ) is 0.60 to 0.80. (11) The method for producing a laminate according to any one of (1) to (10), wherein the method for forming the A layer is a vacuum deposition method, and the method for forming the B layer is selected from a sputtering method, a cluster ion beam method, an ion plating method, an ALD method, and a CVD method. (12) The method for producing a laminate according to (11), wherein the method for forming the layer A comprises a step of simultaneously vacuum-depositing two or more metal compounds. (13) The method for producing a laminate according to (10), comprising the step of forming the layer B and then subsequently forming the layer A. (14) A flexible device using the laminate according to any one of (1) to (10). (15) A solar cell using the laminate according to any one of (1) to (10). (16) An optical sensor using the laminate according to any one of (1) to (10). [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a laminate that has a high level of gas barrier property and high flexibility even with a simple structure. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a cross-sectional view showing an example of a laminate according to the present invention. [Figure 2] 1 is a cross-sectional view showing an example of a laminate according to the present invention. [Figure 3] FIG. 1 is a schematic diagram illustrating an example of a winding-type electron beam vapor deposition apparatus for producing the laminate of the present invention. [Figure 4] FIG. 2 is a top view schematically showing the arrangement of materials for producing the laminate of the present invention. [Figure 5] 1 is a cross-sectional view schematically showing a material arrangement for producing a laminate of the present invention. [Figure 6] FIG. 1 is a schematic diagram illustrating an example of a winding-type electron beam vapor deposition apparatus for producing the laminate of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below.

[0014] [Laminate] A preferred embodiment of the laminate of the present invention is a laminate having an A layer on at least one side of a substrate and a B layer between the substrate and the A layer, wherein the A layer contains at least two metal elements selected from the group consisting of Mg, Si, Zn, Ti, Al, Ce, Sc, and Sr, and oxygen, and the B layer contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, and oxygen, and the B layer has a thickness of less than 10 nm and is 10% or less of the A layer.

[0015] Layer A preferably contains at least two metal elements selected from the group consisting of Mg, Si, Zn, Ti, Al, Ce, Sc, and Sr. Although Si is sometimes called a semimetal, it is classified as a metal element here. Oxides of these metal elements are likely to form thin films with amorphous or fine crystalline structures through vapor deposition. For example, Si and Al have a steep slope of their vapor pressure curves relative to temperature changes, which leads to rapid cooling during and after film formation, making them prone to forming amorphous films. Meanwhile, Mg, Zn, Ti, Ce, Sc, and Sr have a high ionization tendency and high material reactivity, making them prone to forming fine crystalline films. By simultaneously depositing two or more metal oxides, the metal oxides complement the gaps between crystals and the voids within the amorphous structure, forming a dense film. From the perspective of gas barrier properties, Layer A more preferably contains Mg and Si. The Mg and Si contained in Layer A preferably form an amorphous film, and from the viewpoint of gas barrier properties, they are preferably contained as at least one compound selected from the group consisting of oxides, nitrides, oxynitrides, and carbides, and among these, it is more preferable that they contain MgO and SiO2.

[0016] The B layer preferably contains at least one metal selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn. Oxides of these metal elements are easily formed into thin films with amorphous or fine crystalline structures by dry processing. For example, Si, Al, and Sn have a steep slope of their vapor pressure curves relative to temperature changes, and the film is rapidly cooled during and after film formation, making them prone to forming amorphous films by sputtering. Meanwhile, Mg, Zn, Zr, Ti, and In have a high ionization tendency and high material reactivity, making them prone to forming fine crystalline films by sputtering. By layering the A layer on such an amorphous or fine crystalline structure, the A layer begins to develop a dense amorphous or fine crystalline structure by imitating the structure of the B layer from the initial stage of film formation, making it easier to form a film structure with excellent gas barrier properties throughout the entire thickness of the A layer.

[0017] For example, films generally formed by vacuum deposition can grow in a sea-island pattern at high deposition rates, resulting in voids and resulting in low density, especially in the portion closest to the substrate. Therefore, by providing a dense B layer between the A layer and the substrate, a dense amorphous structure or a fine crystalline structure can be formed in layers imitating the structure of the B layer from the early stages of A layer deposition, facilitating the formation of a dense film with excellent gas barrier properties. From the perspective of film formation of the A layer, it is more preferable for the B layer to contain Mg and Si. The Mg and Si contained in the B layer preferably form an amorphous film, and from the perspective of gas barrier properties, it is preferable for them to be contained as at least one compound selected from the group consisting of oxides, nitrides, oxynitrides, and carbides. Among these, it is even more preferable for the B layer to contain MgO and SiO2.

[0018] In the present invention, the order of the layers is preferably the substrate, layer B, and layer A. Layer A contains Mg, Si, Zn, Ti, Al, Ce, Sc, Sr, and oxygen to form a dense composite compound and exhibit gas barrier properties. From the viewpoint of densification, a more preferred embodiment contains Mg, Si, Zn, Al, and oxygen. Even more preferably, it contains Mg, Si, and oxygen. It is preferable to form layer B between the substrate and layer A, as this can promote densification of the composite oxide of these metal elements present in layer A. If layer A and layer B are interchanged, the desired densification promotion effect and gas barrier properties may not be obtained.

[0019] As long as the substrate, layer B, and layer A are present in this order, other layers may be present between the substrate and layer B. For example, an anchor coat layer may be provided between the substrate and layer B to smooth the substrate. Furthermore, a wet coat layer or dry coat layer may be provided on layer A to further improve gas barrier properties, chemical resistance, and scratch resistance. It is preferable that layer A and layer B are adjacent to each other.

[0020] From the viewpoint of transparency, the laminate of the present invention preferably has a total light transmittance of 85% or more. When used in a solar cell member, more efficient power generation becomes possible, so the total light transmittance is preferably 85% or more. Furthermore, from the viewpoint of visibility, the average reflectance in the visible light region (380 to 780 nm) is preferably 15% or less. When used in a solar cell member, more efficient power generation becomes possible, so the average reflectance in the visible light region (380 to 780 nm) is preferably 15% or less.

[0021] The laminate of the present invention has a water vapor permeability of 5.0×10 -3 g / m 2 From the viewpoint of use in packaging materials and electronic device applications that require relatively high gas barrier properties, the water vapor transmission rate of the laminate of the present invention is preferably less than 1.0×10 -3 g / m 2 Although there is no particular lower limit to the water vapor transmission rate, if the film becomes too dense, cracks are likely to occur. Therefore, the water vapor transmission rate of the laminate of the present invention is preferably 1.0×10 -4 g / m 2 / day or more. The water vapor transmission rate is measured by the method described in the examples.

[0022] [A layer] In the laminate of the present invention, the degree of oxidation of the average composition of the layer A, which is represented by the following formula, is preferably 0.9 to 1.7.

[0023] Formula Oxidation degree=X / ((b1 / a1)×Y1+(b2 / a2)×Y2+...) When the average composition (atm %) of Layer A in the present invention is evaluated by X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by analysis is X, the element ratios of metal elements M1, M2, etc. are Y1, Y2, etc., and the composition ratio of the most stable oxides of each metal element in the atmosphere is M:O = a:b, the oxidation degree of the average composition of Layer A is calculated as X / ((b1 / a1) × Y1 + (b2 / a2) × Y2 +...). The peaks used in the analysis are 1s for magnesium, 2p for silicon, 1s for oxygen, 2p for aluminum, 2p for zinc, 2p for calcium, 3d for zirconium, 2p for titanium, 3d for cerium, 2p for scandium, and 3d for strontium. Table 1 shows the oxides composed of each metal element and oxygen that are stable in the atmosphere, along with the coefficient (b / a) used in the calculation formula for the oxidation degree obtained from their composition ratios.

[0024] [Table 1]

[0025] When the oxidation degree in the average composition of Layer A is in the range of 0.9 to 1.7, it is possible to obtain a laminate that is highly transparent and has high gas barrier properties even when it is thin. Details will be described later.

[0026] Layer A preferably contains at least two elements selected from the group consisting of Mg, Si, Zn, Ca, Zr, Ti, Al, Ce, Sc, and Sr, and more preferably contains at least two elements selected from the group consisting of Mg, Si, Zn, Ca, and Al. From the viewpoint of gas barrier properties, layer A more preferably contains Mg and Si.

[0027] The phrase "Layer A contains at least two elements selected from the group consisting of Mg, Si, Zn, Ca, Zr, Ti, Al, Ce, Sc, and Sr, and oxygen" means that, when X-ray photoelectron spectroscopy (XPS) composition analysis is performed while argon etching in 2 nm increments (SiO2 equivalent) from the outermost surface of Layer A toward the substrate under the conditions described in the Examples, the average composition of the element in question is 2.0 atm% or more out of 100.0 atm% of all atoms constituting Layer A. The elemental analysis method used in the XPS evaluation is as described in the Examples.

[0028] Furthermore, if the laminate contains two or more layers that satisfy the conditions for Layer A, those layers are treated separately as Layer A 1, Layer A 2, etc., and the average composition of each Layer A is calculated. If at least one of the Layer A layers is on at least one side of Layer B and the oxidation degree of the average composition of that Layer A is 0.9 to 1.7, the laminate is considered to have Layer A, and the Layer A contains at least two metal elements selected from the group consisting of Mg, Si, Zn, Ti, Al, Ce, Sc, and Sr, as well as oxygen, and the oxidation degree of the average composition of the Layer A, represented by the following formula, is 0.9 to 1.7.

[0029] An oxidation degree of 1 indicates that the metal elements in Layer A are completely oxidized in terms of composition ratio. However, when Layer A is formed by kinetic growth using vacuum deposition, the element distribution within the film is thought to be uneven, and even when the oxidation degree is 1, there may be a mixture of oxygen-excessive, under-oxidized, and completely oxidized areas. Because of this mixed state, in conventional products with low oxidation degrees, some of the metal elements in Layer A are not oxidized, reducing oxygen-mediated bonding. This increases the voids in the amorphous structure, creating pathways for water molecules to permeate, potentially reducing gas barrier properties. Furthermore, when the oxidation degree of Layer A is low in its average composition, there are likely many unoxidized metal elements. These unoxidized metal elements may react with oxygen or water, causing crystallization and expansion of Layer A. Furthermore, the expansion and crystallization of Layer A can change the structure of Layer A itself, resulting in large grain boundaries and cracks, creating pathways for oxygen and water vapor to permeate, potentially reducing gas barrier properties in high-temperature, high-humidity environments. The non-oxidized metal elements may cause the A layer to develop a color, which may reduce the total light transmittance of the gas barrier film.

[0030] On the other hand, if the degree of oxidation is high, it is thought that there are oxygen atoms and oxygen ions in layer A that do not contribute to bonding. Here, the presence of oxygen atoms and ions that do not contribute to bonding causes a charge imbalance, attracting metal atoms in the barrier layer and narrowing the interstitial gaps, improving the barrier layer. Furthermore, the barrier layer becomes amorphous through kinetic film formation, and the oxygen atoms and ions that do not contribute to bonding act as bridges between multiple amorphous network structures, narrowing the gaps and further improving gas barrier properties.

[0031] From the above viewpoints, in a preferred embodiment of the present invention, the oxidation degree in the average composition of Layer A is in the range of 0.9 to 1.7. If the oxidation degree in the average composition of Layer A is less than 0.9, water may break the bonds of the inorganic compounds in Layer A, changing the structure of Layer A and resulting in reduced gas barrier properties. Furthermore, if the oxidation degree in the average composition of Layer A is less than 0.9, oxygen deficiency may cause voids in the amorphous structure of Layer A, resulting in reduced gas barrier properties. Furthermore, non-oxidized metal elements in Layer A may chemically react with water molecules in a humid environment, lengthening the bond distance of atoms in the gas barrier layer and creating voids through which water molecules can pass, or the gas barrier layer may crystallize and change in volume, resulting in deformation or destruction of the barrier layer and significantly reducing gas barrier properties. Furthermore, the non-oxidized metal elements may color Layer A, reducing its total light transmittance. Therefore, the oxidation degree of the average composition of Layer A is preferably 0.9 or more, and if the oxidation degree of the average composition of Layer A exceeds 1.7, oxygen atoms and oxygen ions in the film may swell the inorganic oxide structure, making the barrier layer coarse and reducing the gas barrier properties. From the same perspective, the oxidation degree of the average composition of Layer A is more preferably more than 1.0 and 1.6 or less, and even more preferably 1.2 or more and 1.6 or less.

[0032] A preferred method for achieving a high oxidation degree as described above is to introduce oxygen gas from a position close to the film formation site during film formation. Taking a vacuum deposition method using a metal oxide as a deposition source as an example of a film formation method, even if the deposition source is originally a metal oxide, the chemical bond between the metal atoms and oxygen may be broken while the deposition source is in a high-energy state after sublimation. Therefore, by introducing oxygen gas from a position close to the film formation site during film formation, the probability that the elements of the deposition material will come into contact with oxygen atoms and be converted back into an oxide-state gas increases, thereby improving the oxidation degree of the average composition of the resulting Layer A.

[0033] That is, in the laminate of the present invention, the layer A is preferably an inorganic oxide layer, and the average composition of carbon elements in the layer A is preferably 10 atm% or less, more preferably 5 atm% or less, and even more preferably 1 atm% or less.

[0034] The method for forming Layer A is not particularly limited, and examples that can be used include vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam deposition, ion plating, atomic layer deposition, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD, laser CVD, thermal CVD, and coating. From the perspective of improving the degree of oxidation, it is more preferable to use sputtering or vacuum deposition, which allow oxygen gas to be introduced during film formation and enable adjustment of the amount of oxygen in the raw materials and the degree of vacuum in the chamber.

[0035] In the laminate of the present invention, the degree of oxidation of the average composition of the interface portion of the layer A is preferably 0.9 to 1.7.

[0036] The interface of layer A is determined by depth direction analysis using X-ray photoelectron spectroscopy (XPS), and when layers A and B are composed of different metal elements, the average metal element amount M A In contrast to M A The depth at which the oxygen concentration in the A layer is 1 / 2 is the interface between the A layer and the B layer, and the range is from the interface between the A layer and the B layer to 6 nm toward the surface of the A layer. In addition, when the A layer and the B layer are composed of the same metal element, the average oxygen content in the A layer is M AO and the oxygen content of layer B, M BO When the amount of oxygen is (M AO +M BO ) / 2 is the interface between the A layer and the B layer, and the range is from the interface between the A layer and the B layer to 6 nm toward the surface of the A layer.

[0037] The measurement results at each composition measurement point in the interface are averaged to obtain the average composition of the interface of Layer A. The specific interface of Layer A and the degree of oxidation at the average composition of the interface of Layer A are determined by the method described in the Examples.

[0038] The oxidation degree of the average composition at the interface of the A layer is preferably 0.9 to 1.7. In the formation of the gas barrier layer (A layer), the A layer is typically formed by gradually building up from the substrate side, so the smoothness and density of the underlying layer are important. Having an oxidation degree of 0.9 or higher at the average composition at the interface of the A layer improves the density of the A layer in the early stages of film formation, and also improves the density of the remaining A layer formed on the surface side of the interface, resulting in better water vapor permeability. Furthermore, the transparency at the interface of the A layer is improved, light reflection at the interface is reduced, and total light transmittance is also improved. If the oxidation degree of the average composition at the interface of the A layer exceeds 1.7, the density at the interface decreases, which in turn reduces the density of the entire barrier layer, potentially resulting in reduced gas barrier properties.

[0039] From the viewpoint of the water vapor transmission rate and total light transmission rate described above, the oxidation degree of the average composition at the interface of Layer A is preferably more than 1.0 and 1.6 or less, and more preferably 1.2 or more and 1.6 or less. As a method for adjusting the oxidation degree of the average composition at the interface of Layer A to 0.9 to 1.7, for example, a method of introducing oxygen from the upstream side as shown in FIG.

[0040] The thickness of the layer A is preferably 10 nm or more and 500 nm or less.

[0041] A thickness of 10 nm or more for Layer A ensures stable gas barrier performance, while a thickness of 500 nm or less makes it difficult for cracks to occur due to stress on Layer A, improving flex resistance and stretchability, and preventing a decrease in the gas barrier performance of the laminate.

[0042] The thickness of the A layer can be measured from a cross-sectional image observed with a transmission electron microscope (TEM).

[0043] From the viewpoint of the water vapor transmission rate and cracking susceptibility described above, the thickness of the A layer is more preferably 100 nm to 250 nm, and even more preferably 100 nm to 200 nm.

[0044] The thickness of the A layer can be adjusted by adjusting the film formation time and film formation rate using various film formation methods such as PVD and CVD.

[0045] The A layer more preferably contains one or more elements selected from the group consisting of Al, Mg, Zn, and Ca, and Si, and even more preferably contains one or more elements selected from the group consisting of Al, Mg, and Zn, and Si.

[0046] The elemental forms of Al, Mg, and Zn have a high tendency to ionize, and these metals react easily with oxygen and moisture in the air. Therefore, when these atoms are present in the barrier layer as simple atoms, they are prone to oxidation and hydroxylation in a humid environment, and the structural changes that accompany these reactions cause crystallization and an increase in volume, which can lead to a decrease in gas barrier properties. Therefore, by providing an excess of oxygen in the gas barrier layer, the number of elemental Al, Mg, and Zn atoms decreases, further improving the barrier film's resistance to humidity and heat.

[0047] From the above viewpoint, it is more preferable that the A layer contains one or more elements selected from Al, Mg, and Zn, and it is particularly preferable that the A layer contains Mg.

[0048] In particular, the A layer preferably contains Mg and Si, and the average composition of the A layer measured by X-ray photoelectron spectroscopy has an Mg element ratio of 5 to 50 atm%, an Si element ratio of 2 to 40 atm%, and an O element ratio of 45 to 75 atm%. The A layer preferably has a Zn content of 30 atm% or less, more preferably 20 atm% or less, even more preferably 5 atm% or less, and particularly preferably 1 atm% or less.

[0049] This composition range ensures a sufficient proportion of silicate bonds, improving density and enabling the development of high gas barrier properties. A silicate bond is a bond between Si and a metal (M) via oxygen (O), and can be expressed as Si-OM.

[0050] From the same viewpoint, it is preferable that the Mg element ratio is 40 atm% or less and / or the Si element ratio is 5 atm% or more and 35 atm% or less, and it is preferable that the Mg element ratio is 35 atm% or less and / or the Si element ratio is 10 atm% or more and 30 atm% or less.

[0051] The A layer has an average composition (atm%) of Mg atoms and Si atoms of the A layer of YA Mg and YA Si When the ratio of Mg atoms to the sum of Si atoms and Mg atoms is YA Mg / (YA Mg +YA Si ) is preferably 0.30 to 0.80.

[0052] By keeping the composition ratio within this range, the amount of non-oxidized metal elements is reduced, preventing the formation of a crystalline layer that is prone to cracking and reducing the deterioration of gas barrier properties in high-temperature, high-humidity environments. Furthermore, the presence of excess oxygen reduces the amount of partially non-oxidized elements, forming an amorphous structure with silicate bonds over a wide area, resulting in a dense structure and achieving high gas barrier properties. Furthermore, the excess oxygen has a negative charge and acts to bridge silicate bonds that are not connected by network bonds, which is expected to further improve gas barrier properties.

[0053] From a similar perspective, YA Mg / (YA Mg +YA Si ) is more preferably 0.35 to 0.80, and further preferably 0.55 to 0.75.

[0054] The laminate of the present invention preferably has a mean annihilation lifetime of positrons (hereinafter sometimes referred to as mean lifetime) of 0.750 ns or less when measured from the A layer side by a positron beam method (thin film compatible positron annihilation lifetime measurement method) (see Chapter I, Section 1 and Chapter V, Section 2 of "The Science of Positron Measurement" (Japan Radioisotope Association)). The positron beam method is one of the positron annihilation lifetime measurement methods, and is a technique for measuring the time (on the order of several hundred ps to several tens of ns) from when a positron is incident on a sample until it annihilates, and for non-destructively evaluating information on the size, number concentration, and size distribution of vacancies of about 0.1 to 10 nm from the annihilation lifetime. A radioisotope ( 22 This method differs significantly from the usual positron annihilation method in that it uses a positron beam instead of Na, making it possible to measure thin films of a few hundred nanometers thick formed on silicon or quartz substrates. From the measurements obtained, the nonlinear least-squares program POSITRONFIT can be used to calculate the average pore radius and number concentration of pores. Sub-nanometer-order pores and the basic skeleton can be obtained by analyzing the average lifetimes of the third and fourth components.

[0055] Here, the third component refers to the average life obtained by selecting an analysis for three components as the measurement conditions for the average life by the positron beam method, and the fourth component refers to the average life obtained by selecting an analysis for four components as the measurement conditions for the average life by the positron beam method. When analyzing using POSITRONFIT, the number of components in POSITRONFIT is determined from the number of peaks obtained in the pore radius distribution curve calculated using the distribution analysis program CONTIN based on the inverse Laplace transform method. The validity of the analysis is determined by the agreement between the average pore radius calculated by POSITRONFIT and the peak position of the pore radius distribution curve of CONTIN. The average life in this invention refers to the average life of the third component.

[0056] If the average lifespan is greater than 0.750 ns, the density of layer A will decrease, and the desired gas barrier properties may not be achieved. From the viewpoint of gas barrier properties, the average lifespan measured by the positron beam method is preferably 0.712 ns or less, and more preferably 0.663 ns or less. Furthermore, although there is no particular limitation on the lower limit of the average lifespan, it is preferably 0.542 ns or more. If the average lifespan is less than 0.542 ns, flexibility may decrease.

[0057] The laminate of the present invention preferably has an average pore radius of 0.135 nm or less when measured from the Layer A side by a positron beam method. If the average pore radius is greater than 0.135 nm, the density of Layer A decreases, and the desired gas barrier properties may not be exhibited. From the viewpoint of gas barrier properties, the average pore radius measured by a positron beam method is preferably 0.130 nm or less, and more preferably 0.129 nm or less. Furthermore, there is no particular restriction on the lower limit of the average pore radius, but it is preferably 0.105 nm or more. If the average pore radius is less than 0.105 nm, flexibility may decrease.

[0058] In the present invention, the mean lifetime measured by the positron beam method can be set to 0.750 ns or less by densely forming a composite oxide film with an appropriate composition ratio on a substrate having an arithmetic mean roughness Ra of 10.0 nm or less. "Densely formed" here means that the oxides are mixed at the atomic level to form a dense network.

[0059] In the layer A of the present invention, the half width of the peak of oxygen atoms (O1s) measured by X-ray photoelectron spectroscopy is preferably 3.25 eV or less. max If the peak intensity is F maxThe O1s peak half-width is the peak width at 0.1 / 2. The narrower the half-width of the O1s peak, the more uniform the bond network structure formed, and the more likely it is to form a dense film. From the viewpoint of bond uniformity and barrier properties, the O1s peak half-width is more preferably 3.00 eV or less, and even more preferably 2.75 eV or less. The lower limit is not particularly limited, but is preferably 1.65 eV or more.

[0060] [Example of manufacturing method for layer A] The method for forming Layer A is not particularly limited, and examples thereof include vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam deposition, ion plating, atomic layer deposition, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD, laser CVD, thermal CVD, and coating. From the viewpoints of production cost, environmental impact, gas barrier properties, and the like, vacuum deposition is preferred. Among vacuum deposition methods, electron beam (EB) deposition and ion beam assisted deposition (IBAD) are even more preferred from the viewpoint of compound deposition.

[0061] Furthermore, a preferred embodiment of the laminate manufacturing method of the present invention includes a step of forming the A layer by vacuum deposition, and the step includes a mechanism for introducing oxygen gas during deposition. This embodiment increases the probability that the deposition material, which has sublimated and broken its chemical bond with oxygen, will come into contact with oxygen atoms and re-transform into an oxide-state gas, thereby improving the oxidation degree of the resulting A layer's average composition. It is preferable to use an oxide as the deposition material. When the oxide evaporates or sublimes, the oxide may be deposited on the substrate while maintaining its oxidized state, thereby increasing the oxidation degree of the A layer's average composition. On the other hand, when a simple metal material is deposited and oxidized using only introduced oxygen gas, collisions between metal atoms and oxygen atoms on the substrate surface or contact between metal vapor gas molecules and oxygen gas molecules in the air are required, making it easier to obtain a barrier layer with a lack of oxygen compared to oxide deposition. Furthermore, the surface diffusion distance of metal atoms is short on the substrate surface, where the temperature is reduced by the cooled main drum, making collisions between oxygen and metal atoms less likely to occur. This may result in a lower oxidation degree, especially at the interface during the initial film formation stage.

[0062] This section shows an example of a method for forming Layer A using a reel-up deposition apparatus (Figure 3) with vacuum deposition. A compound thin film of materials C and D is formed on the surface of substrate 1 as Layer A by electron beam (EB) deposition. First, granular materials C and D, approximately 1 to 10 mm in size, are placed as shown in Figures 4 and 5. The deposition materials are not limited to granules; rectangular or tablet-shaped compacts may also be used. The deposition source materials may be arranged in a ratio of materials C and D to obtain the desired film structure for Layer A, or a premix of the two materials may be used. Furthermore, moisture absorption in the deposition material may result in the incorporation of moisture into Layer A, potentially preventing the desired film composition and physical properties. Therefore, it is preferable to dehydrate the material by heating before use. In the reel-up chamber 6, the surface of the substrate 1 on which Layer A is to be formed is set on unwind roll 7 so that it faces hearth liner 12. The substrate is then unwound and passed through guide rolls 8, 9, and 10 onto main drum 11. Next, the pressure inside the deposition device 5 was reduced by a vacuum pump to 5.0×10-3 The ultimate vacuum is 5.0×10 Pa or less. -3 The ultimate vacuum is preferably 5.0 x 10 Pa or less. -3 If the pressure is higher than Pa, residual gas may be trapped in the A layer, making it impossible to obtain the desired film composition and physical properties. -2 Pa or more 5×10 -1 The pressure is controlled to a range of 0.1 Pa or less. Introducing oxygen into the deposition chamber during film formation increases the probability that the deposition material, which has sublimated and broken its chemical bond with oxygen, will come into contact with oxygen atoms and revert to an oxidized gas, thereby improving the oxidation level of the resulting average composition of the A layer. In particular, introducing oxygen into the deposition apparatus 5 through the oxygen introduction gas line 22 increases the probability that the deposition material will revert to an oxidized gas at the film formation location, further improving the oxidation level at the initial stage of film formation (the portion closer to the substrate) near the nozzle of the oxygen introduction gas line. The temperature of the main drum 11 is set to, for example, -10°C. From the viewpoint of preventing thermal damage to the substrate, a temperature of 20°C or less is preferred, and a temperature of 0°C or less is more preferred. Next, using one electron gun (hereinafter referred to as EB gun) 14 as a heating source, the EB gun has an acceleration voltage of 30 kV. The acceleration current and film transport speed are adjusted so that the thickness of the A layer to be formed is approximately 100 to 200 nm, and the A layer is formed on the surface of the substrate 1. The film is then taken up by a take-up roll 19 via guide rolls 16, 17, and 18.

[0063] [B layer] The laminate of the present invention preferably has a layer B between the substrate and the layer A, and the layer B preferably contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, and oxygen.

[0064] The laminate of the present invention has a layer B between the substrate and layer A, and the layer B contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, as well as oxygen, so that the layer A forms a film by imitating the amorphous or fine crystalline structure of layer B, thereby facilitating the formation of an amorphous film of layer A and achieving superior barrier properties. Layer B preferably contains Mg and Si, and the inclusion of Mg, Si, and oxygen makes it easier to control the film hardness, making the layer B less susceptible to cracking due to heat or external stress, and enabling the layer B to consistently achieve excellent density.

[0065] In the present invention, the layer B is preferably a silicon compound, and the silicon compound may include silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, or a mixture thereof. In particular, the layer B preferably includes at least one silicon compound selected from the group consisting of silicon oxide, silicon carbide, silicon nitride, and silicon oxynitride.

[0066] In the present invention, Layer B contains a metal oxide of one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, and silicon oxide, which tends to give the entire film an amorphous structure formed of fine particles, resulting in a laminate with higher gas barrier properties. By containing magnesium oxide and silicon oxide, Layer B can control the flexibility of the film, which is believed to be able to relieve stress generated between the substrate and Layer A due to handling or impact, thereby suppressing the occurrence of defects and cracks in Layer A and consistently achieving high gas barrier properties. It is particularly preferred that Layer B contains one or more metal elements selected from the group consisting of Al, Mg, Zn, In, Sn, and Si, as well as oxygen.

[0067] Layer B contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, meaning that when evaluated by X-ray photoelectron spectroscopy (XPS), the metal element content is 2.0 atm% or more in the area subjected to argon ion etching. If Layer A or other layers are stacked on Layer B, the thickness of the inorganic or organic layer measured by cross-sectional observation with a transmission electron microscope (TEM) is removed by ion etching or chemical treatment, and then analyzed using the method described above.

[0068] With regard to the composition (atm %) of Layer B in the present invention, in order to suppress the occurrence of defects and cracks in Layer A, when evaluated by X-ray photoelectron spectroscopy, it is preferable that the elemental ratio of oxygen obtained by analysis is 50 atm % or more and 80 atm % or less.

[0069] If the oxygen element ratio is less than 50 atm%, the metal oxide may be insufficiently oxidized, resulting in a decrease in light transmittance. Furthermore, if the oxygen element ratio is more than 80 atm%, excessive oxygen is incorporated, resulting in an increase in voids and defects, which may result in a decrease in gas barrier properties. From the viewpoint of controlling the film hardness of Layer B, the oxygen element ratio is more preferably 55 atm% or more and 70 atm% or less.

[0070] That is, in the laminate of the present invention, the layer B is preferably an inorganic oxide layer, and the carbon element content in the layer B is preferably 10 atm% or less, more preferably 5 atm% or less, and even more preferably 1 atm% or less.

[0071] The layer B of the laminate of the present invention contains magnesium and silicon elements in order to form an amorphous structure, and the element ratio of magnesium element is YB Mg (atm%), the elemental ratio of silicon is YB Si (atm%), the ratio of Mg atoms to the sum of Si atoms and Mg atoms, YB Mg / (YB Mg +YB Si ) is 0.60 <YB Mg / (YB Mg +YB Si )<0.80. From the viewpoint of controlling the flexibility and film density of the B layer, it is preferable that the <YB Mg / (YB Mg +YB Si )<0.75 is more preferred.

[0072] YB Mg / (YB Mg +YB Si If YB ≦0.60, the proportion of silicate bonds in the A layer increases, making it easier for random bonds to form, which may increase defects. Mg / (YB Mg +YB Si If )≧0.80, the layer is likely to contain a single crystal of MgO, which reduces flexibility and makes cracks more likely to occur, resulting in a decrease in density and failure to exhibit gas barrier properties.

[0073] The thickness of the B layer is preferably less than 10 nm, more preferably 7.5 nm or less. The laminate of the present invention includes the B layer. For example, when forming an A layer on the surface of the B layer by vacuum deposition, the evaporated material particles forming the A layer strongly bond with the metal elements on the B layer surface. Therefore, after deposition on the B layer surface, the material particles forming the A layer do not diffuse across the B layer surface, and film formation proceeds in a layered manner, resulting in the formation of a highly dense A layer. Furthermore, by having a B layer less than 10 nm, even if a void-containing B layer is formed, the voids can be filled by forming an A layer on the B layer, resulting in a laminate with excellent gas barrier properties. If the B layer is thicker than 10 nm, stress generated between the A layer and the B layer can cause defects in the A layer, and the flexibility of the dense B layer, in particular, can be reduced, making it more susceptible to cracking, resulting in insufficient gas barrier properties. Furthermore, the thickness of the B layer is preferably 1.0 nm or more, more preferably 3.0 nm or more. If the B layer is thicker than 1.0 nm, adhesion between the substrate and the B layer may be insufficient, resulting in insufficient gas barrier properties. Therefore, the thickness of the B layer is preferably 1.0 nm or more and less than 10 nm, and more preferably 3.0 nm or more and 7.5 nm or less.

[0074] Furthermore, from the viewpoint of promoting the formation of a highly dense A layer, the thickness of the B layer is preferably 10% or less of the thickness of the A layer, and from the viewpoint of flexibility, it is preferably 7.5% or less, and from the viewpoint of low-cost formation, it is more preferably greater than 1.0% and less than 5.0%.

[0075] The thickness of Layer B in the present invention is determined by cross-sectional observation using a transmission electron microscope (TEM), as described in detail in the Examples. The composition of Layer B can be determined by X-ray photoelectron spectroscopy (XPS). When Layer A or a resin layer is laminated on Layer B, the thickness of the inorganic layer or resin layer measured by cross-sectional observation using a transmission electron microscope is removed by ion etching or chemical treatment, and then the analysis is performed using the method described above.

[0076] [Manufacturing method for layer B] The method for forming the B layer is not particularly limited, and examples thereof include vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam deposition, ion plating, atomic layer deposition, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD, laser CVD, thermal CVD, and coating. When the B layer contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, it is preferable to form the B layer by vacuum deposition, sputtering, cluster ion beam deposition, ion plating, atomic layer deposition (ALD), or CVD using a mixed sintering material adjusted to the desired composition. Forming the B layer by sputtering, cluster ion beam deposition, ion plating, atomic layer deposition (ALD), or CVD is more preferable, as it allows for the B layer to be dense and allows for the formation of a dense amorphous structure or fine crystalline structure by imitating the structure of the B layer from the initial stage of deposition of the A layer formed on top of it. Among these, the sputtering method is more preferable as it allows the substrate and layer B to exhibit excellent adhesion.

[0077] Next, an example of a method for forming layer B using the winding-type vapor deposition apparatus shown in Figure 3 is shown. A compound thin film of materials C and D is formed as layer B on the surface of substrate 1 by sputtering. First, a sputtering target material 20, in which materials C and D are sintered in the desired composition ratio, is attached to sputtering electrode 21. In winding chamber 6, the surface of substrate 1 on which layer B is to be formed is set on unwinding roll 7 so that it faces sputtering electrode 21. Next, a vacuum pump is used to evacuate vapor deposition apparatus 5 to a pressure of 5.0 x 10 -3 The pressure is reduced to below 1 Pa, and the temperature of guide roll 10 is cooled to, for example, below 0°C. Next, the film is unwound and passed through guide rolls 8, 9, and 10 onto main drum 11. At this time, argon gas and oxygen gas are introduced, and power is applied from a power source to sputtering electrode 21 to generate argon-oxygen gas plasma. The power of the sputtering power source and the film transport speed are adjusted to achieve the desired thickness of layer B, and layer B is formed on the surface of substrate 1. Thereafter, the film is taken up onto take-up roll 19 via guide rolls 16, 17, and 18.

[0078] When forming the B layer and the A layer continuously, the B layer is formed on the surface of the substrate 1, and then the A layer is formed on the B layer by the above-mentioned A layer manufacturing method, and then the resulting product is taken up on the take-up roll 19 via guide rolls 16, 17, and 18.

[0079] That is, in a preferred embodiment of the method for producing a laminate according to the present invention, the method for forming the layer A includes a step of simultaneously vacuum-depositing two or more types of metal compounds.

[0080] [Base material] The substrate used in the present invention is preferably in the form of a film in order to ensure flexibility. The film may be a single-layer film or a film of two or more layers, for example, formed by a co-extrusion method. The type of film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.

[0081] The material of the substrate used in the present invention is not particularly limited, but it is preferable that the substrate is primarily composed 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, polystyrenes, polyvinyl alcohols, saponified ethylene-vinyl acetate copolymers, polyacrylonitriles, polyacetals, and other polymers. Among these, amorphous cyclic polyolefins or polyethylene terephthalates, which have excellent transparency, versatility, and mechanical properties, are preferred. The organic polymer may be either a homopolymer or a copolymer. A single organic polymer may be used, or multiple organic polymers may be blended.

[0082] The surface of the substrate on which Layer B is formed may be subjected to pretreatment such as corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or treatment to form an anchor coat layer made of an organic or inorganic substance or a mixture thereof in order to improve adhesion and smoothness. Also, on the side opposite to the side on which Layer A is formed, a coating layer made of an organic or inorganic substance or a mixture thereof may be laminated in order to improve the slipperiness of the substrate during winding and the scratch resistance of the substrate.

[0083] The thickness of the substrate used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and is preferably 5 μm or more from the viewpoint of ensuring strength against tension and impact. Furthermore, from the viewpoint of ease of processing and handling of the film, the thickness of the substrate is more preferably 10 μm or more and 150 μm or less.

[0084] [Anchor coat layer] The laminate of the present invention preferably has an anchor coat layer, one side of which is in contact with the substrate and the other side of which is in contact with the Layer A. Furthermore, it is more preferable that the anchor coat layer contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. If defects such as protrusions or scratches exist on the substrate, pinholes or cracks may form in the Layer A laminated on the substrate from the defects, impairing the gas barrier properties and flex resistance. Therefore, it is preferable to provide an anchor coat layer. Furthermore, if the difference in thermal dimensional stability between the substrate and Layer A is large, the gas barrier properties and flex resistance may also be reduced, so it is preferable to provide an anchor coat layer. Furthermore, from the viewpoint of thermal dimensional stability and flex resistance, the anchor coat layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure, and more preferably further contains an ethylenically unsaturated compound, a photopolymerization initiator, an organosilicon compound, and / or an inorganic silicon compound.

[0085] The polyurethane compound having an aromatic ring structure used in Layer A of the laminate of the present invention has an aromatic ring and a urethane bond in the main chain or side chain, and can be obtained, for example, by polymerizing an epoxy (meth)acrylate, a diol compound, or a diisocyanate compound having a hydroxyl group and an aromatic ring in the molecule.

[0086] Epoxy (meth)acrylates having a hydroxyl group and an aromatic ring in the molecule can be obtained by reacting a diepoxy compound of an aromatic glycol such as bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, resorcinol, or hydroquinone with a (meth)acrylic acid derivative.

[0087] The component ratios of the epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule, the diol compound, and the diisocyanate compound are not particularly limited as long as they are within a range that results in the desired weight-average molecular weight. The weight-average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. A weight-average molecular weight (Mw) of 5,000 to 100,000 is preferred because the resulting cured film has excellent thermal dimensional stability and flex resistance. The weight-average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted into standard polystyrene.

[0088] The content of the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, it is preferably in the range of 5 to 90 mass %, and more preferably in the range of 10 to 80 mass %, of the total amount including the polyurethane compound having an aromatic ring structure (100 mass %).

[0089] The photopolymerization initiator is not particularly limited as long as it can maintain the gas barrier properties and flex resistance of the laminate of the present invention.

[0090] From the viewpoint of curability and surface protection performance, a photopolymerization initiator selected from 1-hydroxy-cyclohexylphenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred. These may be used as a single composition or as a mixture of two or more components.

[0091] The content of the photopolymerization initiator is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10 mass % of the total amount of polymerizable components, and more preferably in the range of 0.1 to 5 mass %.

[0092] From the viewpoint of curability and polymerization activity upon irradiation with active energy rays, at least one organosilicon compound selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is preferred. These may be used in a single composition or in a mixture of two or more components.

[0093] The content of the organosilicon compound is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10 mass % of the total amount of polymerizable components, and more preferably in the range of 0.1 to 5 mass %.

[0094] As the inorganic silicon compound, silica particles are preferred from the viewpoints of surface protection performance and transparency, and the primary particle diameter of the silica particles is preferably in the range of 1 to 300 nm, more preferably in the range of 5 to 80 nm. Note that the primary particle diameter here refers to the particle diameter d calculated by applying the specific surface area s calculated by the gas adsorption method to the following formula (1):

[0095] d=6 / ρs (1) ρ: Density.

[0096] The thickness of the anchor coat layer is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 2,000 nm or less, and even more preferably 500 nm or more and 1,000 nm or less. If the thickness of the anchor coat layer is thinner than 200 nm, the adverse effects of defects such as protrusions and scratches on the substrate may not be suppressed. If the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer decreases, and the unevenness of the surface of Layer A laminated on the anchor coat layer increases. This makes it difficult to achieve a dense vapor-deposited film, which may make it difficult to achieve improved gas barrier properties. The thickness of the anchor coat layer can be measured from cross-sectional images observed using a transmission electron microscope (TEM).

[0097] The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. Setting Ra to 10 nm or less facilitates the formation of a uniform A layer on the anchor coat layer, improving the repeatability and reproducibility of gas barrier properties, which is desirable. If the Ra of the surface of the anchor coat layer exceeds 10 nm, the unevenness of the A layer surface on the anchor coat layer also increases, making it difficult to achieve a dense vapor-deposited film and making it difficult to obtain improved gas barrier properties. Furthermore, cracks are likely to occur due to stress concentration in areas with many irregularities, which may result in a decrease in the repeatability and reproducibility of gas barrier properties. Therefore, in the present invention, the Ra of the anchor coat layer is preferably 10 nm or less, more preferably 5 nm or less. The Ra of the anchor coat layer in the present invention can be measured using a cross-sectional TEM.

[0098] When applying an anchor coat layer to the laminate of the present invention, an example of a means for applying a coating liquid containing a resin that forms an anchor coat layer containing a polyurethane compound having an aromatic ring structure is to first adjust the solids concentration of a coating material containing a polyurethane compound having an aromatic ring structure onto a substrate so that the thickness after drying is the desired thickness, and then apply the coating material by, for example, reverse coating, gravure coating, rod coating, bar coating, die coating, spray coating, spin coating, etc. Furthermore, in the present invention, from the viewpoint of coating suitability, it is preferable to dilute the coating material containing a polyurethane compound having an aromatic ring structure with an organic solvent.

[0099] [Other layers] The laminate of the present invention may be formed with an overcoat layer or a sealing resin layer for the purpose of improving scratch resistance, chemical resistance, printability, etc., within the range where gas barrier properties and water vapor permeability are not reduced, or may have a laminated structure in which an adhesive layer or film made of an organic polymer compound is laminated for bonding to an element, etc. Also, a low refractive index layer may be formed to improve optical properties. In particular, from the viewpoint of transparency and conductivity, a transparent electrode layer can also be used as an electrode for a solar cell or an organic light-emitting element.

[0100] As long as Layer B fulfills the above functions, it may also serve as an overcoat layer, a sealing resin layer, an adhesive layer, and a low refractive index layer. The overcoat layer and the sealing resin layer may be formed on either side of the laminate.

[0101] [Applications of laminates] The laminate of the present invention has both high light transmittance and gas barrier properties, and therefore can be suitably used in optical elements such as electronic paper and organic electroluminescence (EL) displays. In addition, it can also be suitably used in solar cells and flexible displays, which will be described later.

[0102] [Solar Cell] A preferred embodiment of the solar cell of the present invention is a solar cell including the laminate. This embodiment allows the solar cell to have high durability and energy conversion efficiency, and also to have excellent appearance quality. In particular, organic solar cells, dye-sensitized solar cells, and perovskite solar cells have low corrosion resistance to water, so it is expected that the use of the laminate of the present invention will provide even greater effects.

[0103] [Flexible Display] A preferred embodiment of the flexible display of the present invention is a flexible display using the laminate or optical laminate described above. This embodiment allows the flexible display to have high durability and excellent appearance quality and color characteristics. [Example]

[0104] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[0105] [Evaluation method] (1) Thickness of each layer The thickness of each layer of the laminate was analyzed using a transmission electron microscope (TEM). Samples for cross-sectional observation were prepared by FIB using a microsampling system (Hitachi, Ltd., FB-2000A) (specifically, based on the method described in "Polymer Surface Processing Science" (by Akira Iwamori), pp. 118-119). The cross-section of the sample for observation was observed using a transmission electron microscope (Hitachi, Ltd., H-9000UHRII) at an accelerating voltage of 300 kV, and the thicknesses of layers A and B of the laminate were measured.

[0106] (2) Average composition of layer A and the interface between layer A, and composition of layer B The composition of layers A and B of the laminate was analyzed using X-ray photoelectron spectroscopy (XPS). The average composition of layer A of the laminate was analyzed by etching 2 nm (equivalent to SiO2 thickness) from the outermost surface of layer A using argon ion etching, and then analyzing the composition. The composition of the depth direction from the outermost layer of layer A to 4 nm (equivalent to SiO2 thickness) was excluded from the analysis because it includes the influence of surface contaminants, and the value was averaged up to the interface between layers A and B. The composition of layer B of the laminate was analyzed by etching 2 nm (equivalent to SiO2 thickness) from the interface between layers A and B to a position where the thickness of layer B is half, and then analyzing the composition.

[0107] The peaks used in the analysis were 1s for magnesium, 2p for silicon, 1s for oxygen, 2p for aluminum, 2p for zinc, 2p for calcium, 3d for zirconium, 2p for titanium, 3d for cerium, 2p for scandium, and 3d for strontium.

[0108] The O1s half-width is the maximum intensity of the peak. max If the peak intensity is F max The XPS measurement conditions were as follows:

[0109] Equipment: PHI5000VersaProbeII (ULVAC-PHI) Excitation X-ray: monochromatic AlKα Analysis range: φ100μm Photoelectron escape angle: 45° Ar ion etching: 2.0 kV, raster size 2 x 2.

[0110] In addition, when layers A and B are composed of different metal elements, the average metal element amount in layer A, M A In contrast to M A The depth where the oxygen concentration is 0.1 / 2 is defined as the interface between the A and B layers, and the range from the interface between the A and B layers to 6 nm toward the surface of the A layer is defined as the interface of the A layer. The average value obtained in this range is used as the average composition of the interface of the A layer. In addition, when the A and B layers are composed of the same metal elements, the average oxygen content M AO and the oxygen content of layer B, M BO When the amount of oxygen is (M AO +M BO ) / 2 was defined as the interface between the A layer and the B layer, and the range from the interface between the A layer and the B layer to 6 nm toward the surface of the A layer was defined as the interface part of the A layer.

[0111] (3) Water vapor permeability The water vapor permeability of the laminate was measured at a temperature of 40°C, humidity of 90% RH, and an area of ​​50 cm 2 Measurements were made under the conditions below using a water vapor transmission rate measuring device (model name: DELTAPERM (registered trademark)) manufactured by Technolox, UK. Two samples were measured per level. The data obtained from the measurements of the two samples were averaged, and the average value was used as the water vapor transmission rate (g / m 2 / day).

[0112] (4) Positron lifetime and pore radius distribution The positron lifetime and pore radius distribution were measured using a positron beam method (thin film positron annihilation lifetime measurement method). The sample to be measured was attached to a 15mm x 15mm square Si wafer, degassed at room temperature, and then irradiated with a positron beam from the A layer side. The measurement conditions were as follows: Equipment: Fuji Invac small positron beam generator PALS200A ·Positron source: 22 Na-based positron beam Gamma ray detector: BaF2 scintillator + photomultiplier tube ·Device constants: 255~278ps, 24.55ps / ch Beam intensity: 1 keV Measurement depth: 0 to 100 nm (estimated) ·Measurement temperature: room temperature Measurement atmosphere: vacuum Measurement count: Approximately 5,000,000 counts The measurement results were analyzed into three or four components using the nonlinear least squares program POSITRONFIT.

[0113] (5)Light transmittance The total light transmittance was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the JIS K7361 (1997) standard.

[0114] (6) Bending test Test pieces measuring 10 cm in length and 10 cm in width were cut out and bent 100,000 times with the gas barrier layer facing inward at a bending radius of 2 mm and a bending angle of 180°. The water vapor transmission rate of the test pieces was measured after the bending test. Two pieces were tested for each level.

[0115] Example 1 (Synthesis of Polyurethane Compounds with Aromatic Ring Structures) A 5-liter, four-neck flask was charged with 300 parts by weight of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., product name: Epoxy Ester 3000A) and 710 parts by weight of ethyl acetate, and the flask was heated to an internal temperature of 60°C. 0.2 parts by weight of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by weight of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. After the addition, the reaction was continued for 2 hours, and then 25 parts by weight of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. The reaction was continued for 5 hours after the addition, yielding a polyurethane compound having an aromatic ring structure and a weight-average molecular weight of 20,000.

[0116] (Formation of anchor coat layer) A polyethylene terephthalate film ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the substrate.

[0117] The coating liquid for forming the anchor coat layer was prepared by blending 150 parts by weight of the polyurethane compound, 20 parts by weight of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), 5 parts by weight of 1-hydroxy-cyclohexylphenyl ketone (manufactured by BASF Japan Ltd., trade name: "IRGACURE" (registered trademark) 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicones Co., Ltd., trade name: KBM-503), 170 parts by weight of ethyl acetate, 350 parts by weight of toluene, and 170 parts by weight of cyclohexanone. The coating liquid was then applied to the substrate using a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, and then subjected to ultraviolet treatment under the following conditions to form a 1 μm thick anchor coat layer. UV treatment equipment: LH10-10Q-G (Fusion UV Systems Japan) · Inlet gas: N2 (nitrogen inert box) UV source: Microwave electrodeless lamp Accumulated light output: 400mJ / cm 2 Sample temperature control: Room temperature.

[0118] (Formation of Layers A and B) Using the winding deposition device shown in Figure 3, a MgO+SiO2 layer with a target thickness of 5 nm was formed as layer B on the surface of the anchor coat layer of the substrate by sputtering, and then a MgO+SiO2 layer with a target thickness of 200 nm was formed as layer A by vacuum deposition, in that order.

[0119] The specific operations are as follows: First, a sputtering target material consisting of magnesium oxide (MgO) and silicon dioxide (SiO2), controlled to a composition ratio of approximately Mg:Si:O = 2:1:4 (atm%), was attached to the sputtering electrode. Next, granular magnesium oxide (MgO) (99.9% purity) and silicon dioxide (SiO2) (99.99% purity) with sizes of approximately 2–5 mm were preheated at 100°C for 8 hours. Next, each material was placed in a carbon hearth liner as shown in Figures 4 and 5. The area ratio of the materials was adjusted to MgO:SiO2 = 1:1. In the take-up chamber, the substrate (with anchor coating) was placed on the unwinding roll so that the side on which Layer B would be formed faced the sputtering electrode. Next, the substrate (with anchor coating and Layer B) was unwound and passed through a guide roll onto the main drum so that the side on which Layer A would be formed faced the hearth liner. The temperature of the main drum was controlled at -10°C. Next, the pressure inside the deposition apparatus was reduced using a vacuum pump, and a 5.0 × 10 -3 Pa or less was obtained.

[0120] The pressure inside the deposition device is 5.0 x 10 -3 After the pressure reached 100 Pa or less, argon and oxygen gases were introduced, and an argon-oxygen gas plasma was generated by applying 1000 W of power to the sputtering power supply using a high-frequency power source. The sputtering power and film feed speed were adjusted to form a B layer on the surface of the anchor coat layer, resulting in a thickness of 5 nm. Next, an electron gun (EB gun) was used as a heating source, and the heating ratio of MgO and SiO2 was controlled to achieve a film composition ratio (atm%) of approximately Mg:Si = 2:1. The EB gun acceleration voltage was set to 10 kV, and the acceleration current and film feed speed were adjusted to form an A layer on the surface of the B layer, resulting in a thickness of approximately 200 nm. The film was then wound onto a take-up roll via a guide roll.

[0121] Subsequently, test pieces were cut out from the resulting laminate and various evaluations were carried out. The results are shown in the table.

[0122] Example 2 A laminate was obtained in the same manner as in Example 1, except that a sputtering target material of magnesium oxide (MgO) + silicon oxide (SiO2) controlled to have a composition ratio of approximately Mg:Si:O = 1.5:1:4 (atm %) was used instead of the sputtering target material of Example 1. The results are shown in the table.

[0123] Example 3 A laminate was obtained in the same manner as in Example 1, except that a sputtering target material of magnesium oxide (MgO) + silicon oxide (SiO2) controlled to have a composition ratio of approximately Mg:Si:O = 4:1:7 (atm %) was used instead of the sputtering target material of Example 1. The results are shown in the table.

[0124] Example 4 A laminate was obtained in the same manner as in Example 1, except that the thickness of Layer B was set to a target of 3 nm. The results are shown in the table.

[0125] Example 5 A laminate was obtained in the same manner as in Example 1, except that the thickness of Layer B was set to 10 nm. The results are shown in the table.

[0126] Example 6 A laminate was obtained in the same manner as in Example 1, except that a sputtering target material of indium oxide (III) In2O3 + tin oxide (IV) SnO2 controlled to have a composition ratio of approximately Sn:In:O = 1:9:16 (atm%) was used instead of the sputtering target material of Example 1. The results are shown in the table.

[0127] Example 7 A laminate was obtained in the same manner as in Example 1, except that an aluminum oxide Al2O3 sputtering target material controlled to have a composition ratio of approximately Al:O = 2:3 (atm %) was used instead of the sputtering target material of Example 1, and further, in forming layer A, magnesium oxide was replaced with aluminum oxide and a deposition material controlled to have a composition ratio of approximately Al:Si = 2:1 (atm %) was used. The results are shown in the table.

[0128] Example 8 A laminate was obtained in the same manner as in Example 1, except that a sputtering target material of zinc oxide ZnO + silicon oxide SiO2 + aluminum oxide Al2O3 controlled to have a composition ratio of about Si:Zn:Al:O = 5.5:16:1:30 (atm%) was used instead of the sputtering target material of Example 1, and further, magnesium oxide was replaced with zinc oxide, and a deposition material controlled to have a composition ratio of about Zn:Si = 2:1 (atm%) was used. The results are shown in the table.

[0129] Example 9 A laminate was obtained in the same manner as in Example 1, except that a silicon oxide (SiO2) sputtering target material controlled to have a composition ratio of approximately Si:O = 1:2 (atm %) was used instead of the sputtering target material of Example 1. The results are shown in the table.

[0130] Example 10 Using the reel-up deposition device shown in Figure 6, a MgO+SiO2 layer with a target thickness of 5 nm as layer B and a MgO+SiO2 layer with a target thickness of 200 nm as layer A were successively formed in this order on the surface of the anchor coat layer of the substrate by vacuum deposition.

[0131] The specific procedure is as follows. First, as deposition materials, granular magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO2 (purity 99.99%) with a size of approximately 2 to 5 mm were preheated at 100°C for 8 hours. Next, each material was set in a carbon hearth liner 12, 25, as shown in Figures 4 and 5. The area ratio of the materials was MgO:SiO2 = 1:1. In the take-up chamber, the substrate (with anchor coating) was set on the unwinding roll so that the side on which Layer B was to be formed faced the hearth liner 25. Next, the substrate was unwound and passed through a guide roll onto the main drum so that the side on which Layer A was to be formed faced the hearth liner 12. During this process, the guide roll 10 and the main drum were controlled to a temperature of -10°C. Next, the pressure inside the deposition apparatus was reduced using a vacuum pump, and a 5.0 × 10-3 Pa or less was obtained.

[0132] The pressure inside the deposition device is 5.0 x 10 -3 After the pressure reached 10 Pa or less, an EB gun was used as a heating source, and the heating ratio of MgO and SiO2 was controlled so that the film composition ratio (atm%) was approximately Mg:Si = 2:1. The EB gun had an acceleration voltage of 10 kV, and the acceleration current and film transport speed were adjusted so that the thickness of the formed B layer was approximately 5 nm and the thickness of the A layer was approximately 200 nm. The B layer was formed on the surface of the anchor coat layer, and the A layer was formed on the surface of the B layer. A laminate was obtained in the same manner as in Example 1, except that the acceleration current of EB gun 27 was adjusted to approximately 1 / 40 or less of the acceleration current of EB gun 14 in order to form a dense B layer. The results are shown in Table 1.

[0133] Example 11 A laminate was obtained in the same manner as in Example 1, except that the thickness of Layer B was targeted to be 1 nm. The results are shown in the table.

[0134] (Comparative Example 1) A laminate was obtained in the same manner as in Example 1, except that layer B of Example 1 was not formed. The results are shown in the table.

[0135] (Comparative Example 2) A laminate was obtained in the same manner as in Example 1, except that in forming the B layer, the thickness was set to 20 nm, and in forming the A layer, the thickness was set to 80 nm. The results are shown in the table.

[0136] (Comparative Example 3) A laminate was obtained in the same manner as in Example 1, except that in forming the A layer, silicon dioxide, which is a deposition material, was not used, and only magnesium oxide was used to form an MgO layer with a target thickness of 200 nm. The results are shown in the table.

[0137] Comparative Example 4 A laminate was obtained in the same manner as in Example 1, except that in forming Layer A, magnesium oxide, which is a deposition material, was not used, and only silicon dioxide was used to form an SiO layer with a target thickness of 200 nm. The results are shown in the table.

[0138] [Table 2-1]

[0139] [Table 2-2]

[0140] [Table 3]

[0141] [Table 4]

[0142] [Table 5] [Industrial Applicability]

[0143] The laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, and the like, and can therefore be usefully used, for example, as a packaging material for foods, medicines, and the like, and as a component for electronic devices such as flat-screen televisions and solar cells, but the uses are not limited to these. [Explanation of symbols]

[0144] 1 Base material 2 A layer 3 B layer 4 Anchor coat layer 5. Winding-type electron beam (EB) deposition equipment 6. Winding Room 7 Unwinding roll 8,9,10 Guide roll on unwinding roll side 11 Main Drum 12,25 Hearthliner 13,26 Evaporation materials 14,27 Electron gun 15,28 Electron beam 16, 17, 18 Winding side guide roll 19 Take-up roll 20 Sputtering target material 21 Sputtering electrode 22 Oxygen gas introduction line 23 Evaporation material C 24 Evaporation Material D

Claims

1. A laminate having an A layer on at least one side of a substrate and a B layer between the substrate and the A layer, wherein the A layer contains at least two metal elements selected from the group consisting of Mg, Si, Zn, Ti, Al, Ce, Sc, and Sr, and an oxygen element, and the B layer contains one or more metal elements selected from the group consisting of Mg, Si, Zn, Zr, Ti, Al, In, and Sn, and an oxygen element, and the B layer has a thickness of less than 10 nm and is 10% or less of the thickness of the A layer.

2. 2. The laminate according to claim 1, wherein the element ratio of oxygen in the layer B is 50 to 80 atm % when the composition in the layer B is evaluated by X-ray photoelectron spectroscopy.

3. 2. The laminate according to claim 1, wherein the mean annihilation lifetime of positrons measured from the A layer side by a positron beam method is 0.750 ns or less.

4. 2. The laminate according to claim 1, wherein the degree of oxidation in the average composition of the layer A represented by the following formula is 0.9 to 1.

7. Formula Oxidation degree = X / ((b1 / a1)×Y1+(b2 / a2)×Y2+...) When the average composition in layer A is evaluated by X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by analysis is designated as X, and the element ratios of metal elements M1, M2, . . . are designated as Y1, Y2, . When the composition ratio of the most stable oxides of each metal element in the atmosphere is M:O = a:b, the degree of oxidation in the average composition of layer A is calculated as X / ((b1 / a1) × Y1 + (b2 / a2) × Y2 + ...). The peaks used in the analysis are 1s for magnesium, 2p for silicon, 1s for oxygen, 2p for aluminum, 2p for zinc, 2p for calcium, 3d for zirconium, 2p for titanium, 3d for cerium, 2p for scandium, and 3d for strontium.

5. 2. The laminate according to claim 1, wherein the degree of oxidation in the average composition of the interface portion of the layer A, represented by the following formula, is 0.9 to 1.7: Formula Oxidation degree = X / ((b1 / a1)×Y1+(b2 / a2)×Y2+...) When the average composition of the interface portion of the A layer is evaluated by X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by analysis is designated as X, and the element ratios of the metal elements M1, M2, . . . are designated as Y1, Y2, . When the composition ratio of the most stable oxides of each metal element in the atmosphere is M:O = a:b, the degree of oxidation in the average composition of the interface portion of layer A is calculated as X / ((b1 / a1) × Y1 + (b2 / a2) × Y2 + ...). The peaks used in the analysis are 1s for magnesium, 2p for silicon, 1s for oxygen, 2p for aluminum, 2p for zinc, 2p for calcium, 3d for zirconium, 2p for titanium, 3d for cerium, 2p for scandium, and 3d for strontium. The interface of the A layer is determined by depth direction analysis using X-ray photoelectron spectroscopy (XPS), and when the A layer and the B layer are composed of different metal elements, the average metal element amount M Ａ In contrast to M Ａ The depth at which the oxygen concentration reaches 1 / 2 is the interface between the A layer and the B layer, and the range is from the interface between the A layer and the B layer to 6 nm toward the surface of the A layer. When the A layer and the B layer are composed of the same metal element, the average oxygen content M ＡＯ and the oxygen content of layer B, M ＢＯ When the amount of oxygen is ＡＯ +M ＢＯ The depth at which the thickness of the layer A is 1 / 2 is the interface between the layers A and B, and the range is from the interface between the layers A and B to 6 nm toward the surface of the layer A.

6. 2. The laminate according to claim 1, wherein the A layer contains at least one element selected from the group consisting of Al, Mg, Zn, and Ca, and Si.

7. 7. The laminate according to claim 6, wherein the A layer contains Mg and Si, and has an Mg element ratio of 5 to 50 atm %, an Si element ratio of 2 to 40 atm %, and an O element ratio of 45 to 75 atm %, as measured by X-ray photoelectron spectroscopy.

8. The A layer has an average composition (atm %) of Mg atoms and Si atoms of the A layer of YA Ｍｇ and Y.A. Ｓｉ When the ratio of Mg atoms to the sum of Si atoms and Mg atoms is Ｍｇ / (YA Ｍｇ +YA Ｓｉ 7. The laminate according to claim 6, wherein the value of (a) is 0.30 to 0.

80.

9. 2. The laminate according to claim 1, wherein the layer B contains at least one element selected from the group consisting of Al, Mg, Zn, In, Sn, and Si.

10. The B layer contains Mg and Si, and the element ratio (atm %) of Mg atoms to Si atoms in the B layer is YB Ｍｇ and YB Ｓｉ When the ratio of Mg atoms to the sum of Si atoms and Mg atoms is Ｍｇ / (YB Ｍｇ +YB Ｓｉ 10. The laminate according to claim 9, wherein the value of (a) is 0.60 to 0.

80.

11. The method for producing a laminate according to any one of claims 1 to 10, wherein the method for forming the A layer is a vacuum deposition method, and the method for forming the B layer is selected from a sputtering method, a cluster ion beam method, an ion plating method, an ALD method, and a CVD method.

12. The method for producing a laminate according to claim 11 , wherein the method for forming the layer A comprises a step of simultaneously vacuum-depositing two or more types of metal compounds.

13. The method for producing a laminate according to claim 10 , further comprising the step of forming the layer A continuously after forming the layer B.

14. A flexible device using the laminate according to any one of claims 1 to 10.

15. A solar cell using the laminate according to any one of claims 1 to 10.

16. An optical sensor using the laminate according to any one of claims 1 to 10.

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