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

Abstract

To provide a laminate with high production efficiency that offers advanced gas barrier properties and light transmittance despite its simple structure, and a flexible device, a solar cell, and an optical sensor each including the same.SOLUTION: A laminate has an A layer on at least one side of a substrate. The A layer includes at least two elements selected from the group consisting of groups 2-5 and groups 12-14 in the periodic table, as well as oxygen. The A layer includes an M region with a degree of oxidation of 0.65-0.90 as expressed in a formula defined in the specification.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminate used as a packaging material for foods and medicines that require high gas barrier properties and total light transmittance, and as a material for electronic components such as solar cells, electronic paper, and organic electroluminescence (EL) displays, and to an optical device using the same. [Background technology]

[0002] Gas barrier films formed by forming an inorganic layer of an inorganic substance (including inorganic oxides) on the surface of a film substrate using physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, or chemical vapor deposition (CVD) methods such as plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition are used as packaging materials for foods and medicines that require the blocking of various gases such as water vapor and oxygen, and as electronic device components such as electronic paper. -2 g / m 2 / day or less is required.

[0003] Furthermore, when gas barrier films are used as components of optical devices such as solar cells and light-emitting devices, these components are required to have high light transmittance in order to increase the efficiency of light reception and emission.

[0004] As one method for achieving both high gas barrier properties and light transmittance, a gas barrier film has been proposed in which organic and inorganic layers are alternately laminated in multiple layers to prevent the occurrence of defects through a hole-filling effect (Patent Document 1), and a gas barrier film with a simple film configuration has been proposed in which a complex oxide film such as a ZnO-SnO2-based film is formed on a film substrate by sputtering using a target whose main components are ZnO and SnO2 (Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2005-324406 A [Patent Document 2] JP 2019-73747 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, as in Patent Document 1, it is possible to develop high barrier properties by alternately laminating organic and inorganic layers in multiple layers, but the reflected light intensity increases and the light transmittance decreases due to the laminated structure of materials with different refractive indexes. In addition, there is a problem that the number of steps increases due to lamination, resulting in poor production efficiency. Furthermore, as in Patent Document 2, the laminate formed by sputtering a complex oxide is mainly made of high refractive index materials such as ZnO-SnO2, and there is a problem that the light transmittance decreases due to reflection at the substrate interface. In addition, depending on the film formation conditions, the composition of the complex oxide changes due to dissociation of metal and oxygen in a metal oxide in a high energy state, and the oxide becomes colored, which further reduces the light transmittance. Furthermore, due to the nature of the manufacturing method, there is a limit to increasing the film formation speed, and there is a problem that the production efficiency decreases.

[0007] In view of the background of the conventional technology, the present invention aims to provide a laminate that has high production efficiency and high gas barrier properties and light transmittance even with a simple configuration, as well as a flexible device, a solar cell, and an optical sensor that use the same. [Means for solving the problem]

[0008] A preferred embodiment of the present invention is as follows. (1) A laminate having a layer A on at least one side of a substrate, the layer A containing at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table, and oxygen, and the degree of oxidation of part M of the layer A, as expressed below, is 0.65 to 0.90. The portion M of the layer A is a region extending from a portion 5 nm deep from the outermost surface of the layer A to a portion 30 nm deep on the surface side from the interface reference plane. The interface reference plane is the point where the metal element content becomes <1.0% for the first time when X-ray photoelectron spectroscopy (XPS) composition analysis is performed while argon etching is performed from the outermost surface of layer A toward the substrate. When the film composition of part M of layer A is evaluated by X-ray photoelectron spectroscopy, the elemental ratio of oxygen obtained by analysis is X, and the elemental ratio of oxygen when it is assumed that the metal elements contained in part M of layer A are completely oxidized, is Y. The degree of oxidation is X / Y. (2) The laminate according to (1), wherein the layer A has an oxidation degree at the interface of 0.80 to 0.90. The interface portion of the A layer refers to a region extending from the interface reference plane of the A layer to a position 30 nm toward the surface side from the interface reference plane of the A layer. (3) The laminate according to (1) or (2), wherein the difference in refractive index between the substrate and Layer A for light with a wavelength of 587.562 nm is 0.20 or less. (4) The laminate according to any one of (1) to (3), further comprising a layer B between the substrate and layer A, the layer A and the layer B being in contact with each other, and a difference in refractive index between the layer A and the layer B at a wavelength of 587.562 nm is 0.20 or less. (5) The laminate according to any one of (1) to (4), wherein the A layer contains one element selected from the group consisting of magnesium (Mg), zinc (Zn), and calcium (Ca), and silicon (Si). (6) The laminate according to (5), wherein the A layer contains magnesium (Mg) and silicon (Si), and has a magnesium (Mg) atomic concentration of 5 to 50 atm%, a silicon (Si) atomic concentration of 2 to 30 atm%, and an oxygen (O) atomic concentration of 45 to 70 atm%, as measured by X-ray photoelectron spectroscopy. (7) The laminate according to (5) or (6), wherein the A layer has a ratio (atm %) of atomic concentrations of magnesium (Mg) atoms to silicon (Si) atoms, Mg / (Mg+Si), of 0.30 to 0.80. (8) Water vapor permeability is 5.0×10 -2 g / m 2 / day or less. The laminate according to any one of (1) to (7). (9) The laminate according to any one of (1) to (8), comprising the base material, the layer A, and the layer C in this order, the layer A and the layer C being in contact with each other, and a difference in refractive index between the layer A and the layer C at light with a wavelength of 587.562 nm is 0.20 or less. (10) The method for producing a laminate according to any one of (1) to (9), further comprising a step of forming the A layer by a vacuum deposition method, the step comprising a mechanism for introducing oxygen gas during deposition. (11) A flexible device using the laminate according to any one of (1) to (10). (12) A solar cell using the laminate according to any one of (1) to (10). (13) An optical sensor using the laminate according to any one of (1) to (10). Effect of the Invention

[0009] According to the present invention, it is possible to provide a laminate which has high production efficiency and exhibits high gas barrier properties and light transmittance even with a simple structure. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view showing another example of the laminate of the present invention. [Diagram 3] FIG. 1 is a schematic diagram showing a winding type electron beam deposition apparatus for producing a laminate of the present invention. [Figure 4] FIG. 2 is a schematic diagram showing an example of an oxygen gas introduction nozzle in a winding type vacuum deposition apparatus for producing the laminate of the present invention. [Diagram 5] FIG. 2 is a diagram showing a schematic top view of the arrangement of materials for producing a laminate of the present invention. [Figure 6] FIG. 2 is a schematic side view showing the arrangement of materials for producing a laminate of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] A preferred embodiment of the present invention will be described in detail below.

[0012] [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, the A layer containing at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table, and oxygen, and the oxidation degree, represented as follows, of part M of the A layer is 0.65 to 0.90.

[0013] The M part of layer A refers to the region from 5 nm from the top surface of layer A to 30 nm on the surface side from the interface reference plane. The interface reference plane refers to the location where the metal element content ratio is <1.0 atm% when X-ray photoelectron spectroscopy (XPS) composition analysis is performed while argon etching from the top surface of layer A toward the substrate. The position 30 nm on the surface side from the interface reference plane is determined from the SiO2 equivalent thickness.

[0014] Regarding the outermost surface of layer A, if no particular layer is formed on the surface of layer A and layer A is in contact with air, the first measurement point in the XPS composition analysis is taken as the outermost surface of layer A. If a layer other than layer A, such as an overcoat layer, exists on the surface of layer A, the measurement point where at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table are first detected is taken as the outermost surface of layer A. The position of the portion 5 nm from the outermost surface of layer A is determined from the SiO2 equivalent thickness.

[0015] The conditions for the XPS composition analysis are as follows: Excitation X-ray: monochromatic AlKα Analysis range: φ100μm Photoelectron escape angle: 45° Ar ion etching: 3.0kV, raster size 2×2. Etching rate: Within 15nm / min (SiO2 equivalent) Etching interval: within 8.7 nm (SiO2 equivalent) per step.

[0016] The degree of oxidation is a value expressed as X / Y, where X is the element ratio of oxygen obtained by analysis of the film composition of part M of layer A evaluated by X-ray photoelectron spectroscopy, and Y is the element ratio of oxygen when it is assumed that at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table contained in layer A are all complete oxides of dioxide. The film composition of part M is the composition averaged from the composition profile of part M when XPS composition analysis is performed.

[0017] As a combination of at least two elements selected from the group consisting of elements of Groups 2 to 5 and Groups 12 to 14 of the periodic table contained in the M part of the A layer, from the viewpoints of gas barrier properties, total light transmittance, forming an amorphous film, etc., it is preferable that the combination is at least two elements selected from the group consisting of magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, silicon, germanium, and tin, and it is more preferable that the at least two elements are either magnesium and silicon, zinc and silicon, or calcium and silicon. From the viewpoint of gas barrier properties, it is even more preferable that the combination is magnesium and silicon. In other words, it is preferable that the M part of the A layer has one or more elements selected from magnesium, zinc, and calcium, it is more preferable that the M part of the A layer contains magnesium and / or calcium, and it is even more preferable that the M part of the A layer contains magnesium.

[0018] The A layer contains oxygen when evaluated by XPS and the oxygen atom content is 10.0 atm% or more at a location where a layer is removed by argon ion etching 5 nm from the outermost surface of the A layer in terms of the equivalent thickness of a SiO2 film. From the viewpoints of light transmittance, denseness, etc., the oxygen atom content is preferably 20.0 atm% or more, and more preferably 40.0 atm% or more.

[0019] The form of at least two elements selected from the group consisting of elements of Groups 2 to 5 and Groups 12 to 14 of the periodic table contained in the M part of the A layer may be oxide, nitride, oxynitride, carbide, etc., but is not particularly limited. From the viewpoint of gas barrier properties and optical properties, it is preferable that the elements are present in the form of oxide, nitride, or oxynitride. From the viewpoint of forming an amorphous film and gas barrier properties, it is more preferable that the elements are contained as at least one compound selected from the group consisting of oxide, nitride, oxynitride, and carbide. As long as the A layer of the laminate of the present invention contains at least two elements selected from the group consisting of elements of Groups 2 to 5 and Groups 12 to 14 of the periodic table and oxygen, other inorganic compounds may be contained.

[0020] Among them, it is preferable that the A layer contains any one of magnesium oxide, zinc oxide, and calcium oxide, and silicon oxide. It is more preferable that the A layer contains magnesium oxide and silicon oxide, from the viewpoint of forming a dense composite oxide film and improving gas barrier properties. When the A layer contains magnesium oxide and silicon oxide, other elements may be contained as long as magnesium oxide and silicon oxide are contained.

[0021] When the film composition of the M part of the A layer is evaluated by X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by the analysis is X, and the element ratio of oxygen when it is assumed that at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table contained in the A layer are all completely oxidized as dioxide is Y. When the oxidation degree X / Y is 0.65 or more, the concentration of metal atoms existing as simple substances in the transparent film is reduced, and the light transmittance is improved. Furthermore, when the oxidation degree X / Y is 0.90 or less, there are fewer isolated atoms between the amorphous structures, the gap of the A layer is narrowed, and the barrier property is also improved. From the same viewpoint, the oxidation degree X / Y is more preferably 0.75 to 0.90, and even more preferably 0.80 to 0.90.

[0022] As a means for achieving the above-mentioned appropriate oxidation degree of the M part of the A layer, it is preferable to use an oxide of the above element as the deposition material, and further introduce oxygen gas, and to appropriately introduce the position, amount, and method of the oxygen gas. When the oxide target of the above element becomes gas by sublimation, ablation, sputtering, etc. in the film formation in vacuum, the chemical bond is broken and it becomes a single atom, and there is a possibility that the oxidation degree of the M part of the A layer decreases. However, by introducing oxygen, the probability that the single atom comes into contact with the oxygen atom and changes again to an oxide increases, and the oxidation degree of the resulting film can be improved. Specifically, in the case of the winding type vacuum deposition device 4 shown in FIG. 3, as an example, the amount of oxygen gas introduced from the oxygen gas introduction nozzle 11b is preferably 0.1 to 19 L / min as the introduction amount of the oxygen gas. The oxygen partial pressure in the deposition chamber increases, and the oxidation degree of the M part of the A layer can be increased. It is preferable to use a nozzle with a tubular shape with a unidirectional introduction direction as shown in FIG. 4. As shown in Figure 4, the gas inlet has a tubular shape, so the gas introduced from the gas inlet has high directionality, making it possible to efficiently oxidize targeted locations.

[0023] In the laminate of the present invention, the difference in refractive index of light having a wavelength of 587.562 nm between the substrate and the A layer is preferably 0.20 or less. By making the difference in refractive index between the substrate and the A layer 0.20 or less, the reflected light intensity at the interface between the A layer and the substrate is reduced, and the light transmittance is improved. The refractive index of the A layer and the substrate can be measured using a high-speed spectroscopic ellipsometer. From the same viewpoint, the difference in refractive index between the A layer and the substrate is more preferably 0.15 or less, and even more preferably 0.10 or less.

[0024] The laminate of the present invention preferably has a B layer between the substrate and the A layer, the A layer and the B layer being in contact with each other, and the difference in refractive index between the A layer and the B layer at a wavelength of 587.562 nm is 0.20 or less. By making the difference in refractive index between the A layer and the B layer 0.20 or less, the reflected light intensity at the interface between the A layer and the adjacent B layer is reduced, improving the light transmittance. The refractive indexes of the A layer and the B layer can be measured using a high-speed spectroscopic ellipsometer.

[0025] The degree of oxidation X / Y of the interface of the A layer of the present invention is preferably 0.80 to 0.90. The interface refers to a region from the interface reference plane of the A layer to a region 30 nm from the interface reference plane of the A layer on the surface side. The degree of oxidation of the interface is a value expressed by X / Y, where X is the element ratio of oxygen obtained when the film composition of the interface of the A layer is evaluated by X-ray photoelectron spectroscopy, and Y is the element ratio of oxygen when it is assumed that at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table contained in the interface of the A layer are all present as complete oxides of dioxide. The film composition of the interface is a value obtained by averaging the composition profile of a region 30 nm from the interface reference plane of the A layer on the surface side by XPS composition analysis while argon etching from the outermost layer side of the A layer toward the substrate.

[0026] The form of at least two elements selected from the group consisting of elements of Groups 2 to 5 and Groups 12 to 14 of the periodic table contained in the A layer interface may be oxide, nitride, oxynitride, carbide, etc., but is not particularly limited thereto. From the viewpoint of gas barrier properties and optical properties, it is preferable that the elements are present in the form of oxide, nitride, or oxynitride. From the viewpoint of forming an amorphous film and gas barrier properties, it is more preferable that the elements are contained as at least one compound selected from the group consisting of oxide, nitride, oxynitride, and carbide. As long as the A layer of the laminate of the present invention contains at least two elements selected from the group consisting of elements of Groups 2 to 5 and Groups 12 to 14 of the periodic table and oxygen, other inorganic compounds may be contained.

[0027] Among them, it is preferable that the A layer interface contains one of magnesium oxide, zinc oxide, and calcium oxide, and silicon oxide. It is more preferable that the A layer interface contains magnesium oxide and silicon oxide, from the viewpoint of forming a dense composite oxide film and improving gas barrier properties. When the A layer interface contains magnesium oxide and silicon oxide, other elements may be contained as long as magnesium oxide and silicon are contained.

[0028] When the film composition of the interface of the A layer is evaluated by X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by the analysis is X, and the element ratio of oxygen when at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table contained in the A layer are all assumed to be complete oxides of dioxide is Y. When the oxidation degree X / Y is in the range of 0.80 to 0.90, the concentration of single atoms present in the entire A layer is reduced and the light transmittance is improved. In addition, the bond of the compound narrows the gap of the A layer, and the barrier property is improved. Furthermore, when the oxidation degree of the interface is in an appropriate range, the refractive index difference at the interface with the anchor coat or the substrate is reduced, and the reflection of light at the interface is reduced, thereby improving the total light transmittance. From the same viewpoint, the oxidation degree X / Y of the interface of the A layer is more preferably 0.85 to 0.90.

[0029] As a method for setting the oxidation degree of the M part of the A layer to 0.65 to 0.90 and the oxidation degree of the interface part of the A layer to 0.80 to 0.90, it is preferable to appropriately introduce the oxygen gas at the position, the amount of introduction, and the method of introduction. Specifically, in the case of the winding type vacuum deposition apparatus 4 shown in FIG. 3, the amount of oxygen gas introduced from the oxygen gas introduction nozzles 11a and 11b during the formation of the A layer is preferably 0.1 to 19 L / min. The oxygen gas introduced from 11a can increase the oxidation degree of the interface part of the A layer at the beginning of the A layer formation, that is, the oxidation degree of the M part can also be increased by the oxygen gas introduced from the oxygen gas introduction nozzle 11b. It is preferable to use the oxygen gas introduction nozzle 11a, like 11b, which has a tubular shape with a unidirectional introduction direction as shown in FIG. 4. By using the tubular shape of the gas introduction port as shown in FIG. 4, the directivity of the gas introduced from the gas introduction port is high, and the targeted position can be efficiently oxidized.

[0030] In the present invention, it is preferable that the absolute value of the difference between the oxidation degree of the portion M of the layer A and the oxidation degree of the interface portion of the layer A is 0.20 or less. By adopting this embodiment, the total light transmittance can be improved.

[0031] The average composition in the thickness direction of the layer A of the present invention is preferably a laminate containing magnesium (Mg) and silicon (Si) as at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and having a magnesium (Mg) atomic concentration of 5 to 50 (atm%), a silicon (Si) atomic concentration of 2 to 30 (atm%), and an oxygen (O) atomic concentration of 45 to 70 (atm%) as measured by X-ray photoelectron spectroscopy. The average composition in the thickness direction of the layer A refers to the average composition ratio from the outermost surface to the interface reference plane when composition analysis is performed by XPS while argon ion etching from the outermost surface of the layer A toward the substrate in SiO2 equivalent thicknesses of 5 nm each.

[0032] With regard to the average composition in the thickness direction of layer A, in order to prevent the layer from becoming a crystalline layer and being susceptible to cracking, it is preferable that the magnesium atomic concentration is 50 atm % or less and / or the silicon atomic concentration is 2 atm % or more.

[0033] With regard to the average composition in the thickness direction of the A layer, it is preferable that the magnesium atom concentration is 5 atm% or more and / or the silicon atom concentration is 30 atm% or less, from the viewpoint of making the ratio of silicate bonds in the A layer sufficient and improving the density to exhibit gas barrier properties. The silicate bond is a bond between silicon (Si) and metal (M) via oxygen (O), and can be written as Si-OM.

[0034] In terms of the average composition in the thickness direction of layer A, in order to prevent magnesium and silicon from being insufficiently oxidized and thus causing a decrease in light transmittance, the oxygen atomic concentration is preferably 45 atm% or more, and in order to prevent an increase in voids and defects caused by excessive oxygen incorporation and to exhibit gas barrier properties, the oxygen atomic concentration is preferably 70 atm% or less.

[0035] From the above viewpoints, the average composition in the thickness direction of Layer A of the present invention is more preferably a magnesium atomic concentration of 8 to 35 (atm%), a silicon atomic concentration of 6 to 25 (atm%), and an oxygen atomic concentration of 50 to 65 (atm%), and even more preferably a magnesium atomic concentration of 15 to 30 (atm%), a silicon atomic concentration of 8 to 20 (atm%), and an oxygen atomic concentration of 50 to 65 (atm%).

[0036] With regard to the average composition in the thickness direction of Layer A of the present invention, the laminate is preferably one in which the atomic concentration (atm%) ratio Mg / (Mg+Si) of magnesium (Mg) atoms to silicon (Si) atoms is 0.30 to 0.75.

[0037] With respect to the average composition in the thickness direction of the A layer, when the atomic concentration (atm%) ratio is Mg / (Mg+Si)≧0.30, the proportion of silicate bonds in the A layer is sufficient, and the density is improved to exhibit gas barrier properties. When the atomic concentration (atm%) ratio is Mg / (Mg+Si)≦0.70, the presence of crystal parts in the A layer is suppressed, and the tendency for cracks to occur can be suppressed. From the same viewpoint, the atomic concentration (atm%) ratio Mg / (Mg+Si) is more preferably 0.35 to 0.70, and even more preferably 0.40 to 0.65.

[0038] The laminate of the present invention has a water vapor permeability of 5.0×10 -2 g / m 2 From the viewpoint of use in high-grade packaging materials and electronic device applications that require relatively high gas barrier properties, the water vapor permeability of the laminate of the present invention is preferably less than 1.0×10 -2 g / m 2 Although there is no particular lower limit to the water vapor permeability, if the film becomes too dense, cracks are likely to occur. Therefore, the water vapor permeability of the laminate of the present invention is preferably 1.0×10 -4 g / m 2 / day or more is preferable.

[0039] [Example of manufacturing method for layer A] The method for forming the A layer is not particularly limited, and may be a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, an atomic layer deposition method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like. From the viewpoints of production cost, environmental load, gas barrier properties, and the like, it is preferable to use a vacuum deposition method. From the viewpoint of compound deposition, it is more preferable to use electron beam (EB) deposition or ion beam assisted deposition (IBAD) among the vacuum deposition methods.

[0040] In addition, a preferred embodiment of the method for producing a laminate of the present invention includes a step of forming the A layer by a vacuum deposition method, and includes a mechanism for introducing oxygen gas during deposition. When the oxide target of the above elements becomes gas by sublimation, ablation, sputtering, etc. in a vacuum film formation, the chemical bonds are broken and the M part of the A layer becomes a single atom, and there is a possibility that the oxidation degree of the M part of the A layer decreases. However, by adopting this embodiment, the probability that the single atom comes into contact with an oxygen atom and changes to an oxide again increases, and the oxidation degree of the resulting film can be improved. Among the elements of Groups 2 to 5 of the periodic table, Mg and Ca are particularly likely to dissociate from oxygen when the oxide becomes highly energetic, so that this embodiment is effective. In addition, if the film formation raw material is heated to a higher temperature, the film formation speed increases and the productivity improves, but the metal oxide is more likely to dissociate into metal and oxygen. However, by introducing oxygen gas, dissociation is suppressed, and film formation can be performed faster than before.

[0041] An example of a method for forming the A layer by a winding type deposition apparatus (FIG. 3) using a vacuum deposition method is shown. A compound thin film of materials B and C is provided as the A layer on the surface of the substrate 1 by electron beam (EB) deposition. First, granular materials B and C having a size of about 5 to 10 mm are arranged as the deposition materials as shown in FIG. 5. The deposition material is not limited to granules, and may be in the form of a molded body such as a square or tablet. In addition, the deposition source material may be arranged in a ratio of materials B and C, or a material in which the two materials are mixed in advance may be used so that the A layer has a desired film structure. In addition, if the deposition material absorbs moisture, the moisture in the material may be taken into the A layer, and the desired film composition and physical properties may not be obtained, so it is preferable to perform a dehydration treatment by heating the material before use. In the winding chamber 5, the surface of the substrate 1 on which the A layer is to be provided is set on the unwinding roll 6 so that it faces the crucible 12, and the substrate is unwound and passed through the main drum 10 via guide rolls 7, 8, and 9. Next, the pressure inside the deposition device 4 was reduced by the vacuum pump to 5.0×10 -3 The ultimate vacuum level is 5.0×10 Pa or less. -3 The ultimate vacuum is preferably 5.0×10 Pa or less. -3 If the pressure is higher than 1 Pa, residual gas may be trapped in the A layer, making it difficult to obtain the desired film composition and physical properties. -2Pa or more was obtained. By introducing oxygen into the film formation chamber during film formation as described above, the probability of contacting with the oxygen atoms of the deposition material that have been sublimated and whose chemical bonds with oxygen have been cut and changing again into a gas in an oxide state increases, and the oxidation degree of the resulting film is improved. The oxygen gas introduced from the oxygen gas introduction nozzle 11a improves the oxidation degree of the A layer interface portion, and the oxygen gas introduced from the oxygen gas introduction nozzle 11b improves the oxidation degree of the A layer M portion. The temperature of the main drum 10 is set to -10°C as an example. From the viewpoint of preventing heat damage to the substrate, it is preferably 20°C or less, and more preferably 0°C or less. Next, one electron gun (hereinafter, EB gun) 14 is used as a heating source, and 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 about 150 nm, and the A layer is formed on the surface of the substrate 1. Thereafter, the film is wound up on a take-up roll 19 via guide rolls 16, 17, and 18.

[0042] [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 having two or more layers, for example, a film 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.

[0043] The material of the substrate used in the present invention is not particularly limited, but it is preferable that the substrate is mainly 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, polystyrene, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymers, polyacrylonitrile, polyacetal, and various other polymers. Among these, it is preferable to use cyclic polyolefins or polyethylene terephthalate, which have excellent light transmittance, versatility, and mechanical properties. In addition, the organic polymer may be either a homopolymer or a copolymer, and only one type of organic polymer may be used, or multiple types may be blended together.

[0044] The surface of the substrate on which the layer A is formed may be pretreated to improve adhesion and smoothness by corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or treatment to form an anchor coat layer composed of an organic or inorganic substance or a mixture thereof. Also, on the side opposite to the side on which the layer A is formed, a coating layer of an organic or inorganic substance or a mixture thereof may be laminated for the purpose of improving the slipperiness during winding of the substrate and the scratch resistance of the substrate.

[0045] 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, the thickness of the substrate is more preferably 10 μm or more and 150 μm or less from the viewpoint of ease of processing and handling of the film.

[0046] [B layer] The laminate of the present invention may have a B layer. The B layer is not particularly limited to a deposition layer other than the A layer or an anchor coat layer. From the viewpoint of flatness and adhesion, it is preferable that it is an anchor coat layer. It is preferable that the anchor coat layer has one surface in contact with the substrate and the other surface in contact with the A layer. Furthermore, it is more preferable that the anchor coat layer contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. When defects such as protrusions or scratches exist on the substrate, pinholes or cracks may occur in the A layer laminated on the substrate starting from the defects, which may impair gas barrier properties and bending resistance, so it is preferable to provide an anchor coat layer. In addition, when the difference in thermal dimensional stability between the substrate and the A layer is large, the gas barrier properties and bending resistance may also decrease, so it is preferable to provide an anchor coat layer. In addition, the anchor coat layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and bending resistance, and more preferably contains an ethylenically unsaturated compound, a photopolymerization initiator, an organic silicon compound and / or an inorganic silicon compound.

[0047] 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.

[0048] An epoxy (meth)acrylate 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 type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, or hydroquinone, with a (meth)acrylic acid derivative.

[0049] Examples of the diol compound include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 1,2-cyclohexane. Dimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4'-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, etc. can be used. These can be used alone or in combination of two or more.

[0050] Examples of the diisocyanate compound include aromatic diisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4-diphenylmethane diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, Examples of the isocyanate include aliphatic diisocyanate compounds such as 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, alicyclic isocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, and methylcyclohexylene diisocyanate, and aromatic aliphatic isocyanate compounds such as xylylene diisocyanate and tetramethylxylylene diisocyanate, etc. These can be used alone or in combination of two or more.

[0051] The component ratio of the epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule, the diol compound, and the diisocyanate compound is not particularly limited as long as it is within a range that results in a 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. If the weight average molecular weight (Mw) is 5,000 to 100,000, the resulting cured film has excellent thermal dimensional stability and bending resistance, which is preferable. The weight average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted into standard polystyrene.

[0052] Examples of ethylenically unsaturated compounds include di(meth)acrylates such as 1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate, polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and epoxy acrylates such as bisphenol A type epoxy di(meth)acrylate, bisphenol F type epoxy di(meth)acrylate, and bisphenol S type epoxy di(meth)acrylate. Among these, polyfunctional (meth)acrylates that are excellent in thermal dimensional stability and surface protection performance are preferred. In addition, these may be used in a single composition, or two or more components may be mixed and used.

[0053] 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 (100 mass%) of the ethylenically unsaturated compound and the polyurethane compound having an aromatic ring structure.

[0054] The photopolymerization initiator is not particularly limited as long as it can maintain the gas barrier property and flex resistance of the laminate of the present invention.The photopolymerization initiator that can be suitably used in the present invention includes, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenyl glyoxylic acid methyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) Examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators such as -butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, titanocene-based photopolymerization initiators such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, and photopolymerization initiators having an oxime ester structure such as 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)].

[0055] Among these, from the viewpoint of curability and surface protection performance, photopolymerization initiators selected from 1-hydroxy-cyclohexyl phenyl 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 are preferred. These may be used in a single composition or in a mixture of two or more components.

[0056] 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 %, and more preferably in the range of 0.1 to 5 mass %, of the total amount of polymerizable components.

[0057] Examples of the organosilicon compound include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatepropyltriethoxysilane.

[0058] Among these, from the viewpoint of curability and polymerization activity by 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.

[0059] 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 %, and more preferably in the range of 0.1 to 5 mass %, of the total amount of polymerizable components.

[0060] As the inorganic silicon compound, silica particles are preferred from the viewpoints of surface protection performance and light transmittance, and the primary particle size 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 size here refers to the particle diameter d calculated by applying the specific surface area s calculated by a gas adsorption method to the following formula (1): d=6 / ρs (1) ρ: Density.

[0061] 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 present 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 uneven shape of the surface of the A layer laminated on the anchor coat layer also becomes large, making it difficult for the laminated vapor deposition film to become dense, and the effect of improving the gas barrier property may be difficult to obtain. Here, the thickness of the anchor coat layer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

[0062] The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. When Ra is 10 nm or less, it is preferable because it is easy to form a homogeneous A layer on the anchor coat layer, and the repeatability reproducibility of the gas barrier property is improved. When the surface Ra of the anchor coat layer is greater than 10 nm, the uneven shape of the A layer surface on the anchor coat layer also becomes large, the evaporated film is difficult to be dense, and the effect of improving the gas barrier property may be difficult to obtain. In addition, cracks due to stress concentration are likely to occur in the part with many unevenness, which may cause a decrease in the repeatability reproducibility of the gas barrier property. Therefore, in the present invention, it is preferable to set the Ra of the anchor coat layer to 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 an atomic force microscope (AFM) or the like.

[0063] When applying an anchor coat layer to the laminate of the present invention, the coating liquid containing the resin that forms the anchor coat layer is preferably applied by first adjusting the solid content concentration of a coating material containing a polyurethane compound having an aromatic ring structure on a substrate so that the thickness after drying is the desired thickness, and then applying the coating material by, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a die coating method, a spray coating method, a spin coating method, etc. In addition, in the present invention, it is preferable to dilute the coating material containing a polyurethane compound having an aromatic ring structure using an organic solvent from the viewpoint of coating suitability.

[0064] Specifically, it is preferable to dilute the coating material to a solid content concentration of 10% by mass or less using a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane, or hexane, or an ether solvent such as dibutyl ether, ethyl butyl ether, or tetrahydrofuran. These solvents may be used alone or in combination of two or more. In addition, various additives may be added to the coating material for forming the anchor coat layer as necessary. For example, catalysts, antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers, surfactants, leveling agents, antistatic agents, etc. may be used.

[0065] Next, it is preferable to dry the coating film after application to remove the dilution solvent. Here, the heat source used for drying is not particularly limited, and any heat source such as a steam heater, an electric heater, or an infrared heater can be used. In order to improve gas barrier properties, the heating temperature is preferably 50 to 150°C. In addition, the heat treatment time is preferably several seconds to 1 hour. Furthermore, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. In addition, the heat treatment may be performed while adjusting the humidity in the range of 20 to 90% RH in terms of relative humidity during the drying treatment. The heat treatment may be performed in the air or while an inert gas is enclosed.

[0066] Next, it is preferable to subject the dried coating film containing a polyurethane compound having an aromatic ring structure to an active energy ray irradiation treatment to crosslink the coating film, thereby forming an anchor coat layer.

[0067] The active energy rays to be applied in such a case are not particularly limited as long as they can cure the anchor coat layer, but it is preferable to use ultraviolet treatment from the viewpoint of versatility and efficiency. As the ultraviolet source, known ones such as high pressure mercury lamps, metal halide lamps, microwave type electrodeless lamps, low pressure mercury lamps, xenon lamps, etc. can be used. In addition, it is preferable to use the active energy rays under an inert gas atmosphere such as nitrogen or argon from the viewpoint of curing efficiency. The ultraviolet treatment may be performed either under atmospheric pressure or under reduced pressure, but in the present invention, it is preferable to perform the ultraviolet treatment under atmospheric pressure from the viewpoint of versatility and production efficiency. Regarding the oxygen concentration during the ultraviolet treatment, the oxygen gas partial pressure is preferably 1.0% or less, more preferably 0.5% or less, from the viewpoint of controlling the crosslinking degree of the anchor coat layer. The relative humidity may be arbitrary.

[0068] As the ultraviolet ray generating source, known sources such as a high pressure mercury lamp, a metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp, etc. can be used.

[0069] The cumulative amount of UV light is 0.1 to 1.0 J / cm 2 is preferably 0.2 to 0.6 J / cm 2 It is more preferable that the integrated light amount is 0.1 J / cm 2 If the integrated light amount is 1.0 J / cm or more, a desired degree of crosslinking of the anchor coat layer can be obtained, which is preferable. 2 If the thickness is less than this, damage to the substrate can be reduced, which is preferable.

[0070] [C layer] The laminate of the present invention preferably has the substrate, the A layer, and the C layer in this order, the A layer and the C layer are in contact with each other, and the difference in refractive index between the A layer and the C layer at a wavelength of 587.562 nm is 0.20 or less. This embodiment reduces the reflected light intensity at the interface between the A layer and the C layer adjacent thereto, improving the light transmittance. The refractive indexes of the A layer and the C layer can be measured using a high-speed spectroscopic ellipsometer. On the A layer of the laminate of the present invention, that is, on the C layer, an overcoat layer may be formed for the purpose of improving printability and adhesion to an adhesive layer, etc., within a range in which the gas barrier properties are not reduced, or a laminated structure in which an adhesive layer or film made of an organic polymer compound for bonding to an element, etc. is laminated may be used. A low refractive index layer may also be formed to improve optical properties.

[0071] [Applications of laminates] The laminate of the present invention has high gas barrier properties and can be suitably used as a gas barrier film. For example, by taking advantage of the high barrier properties, it can be suitably used as an exterior part of a lithium ion battery or a packaging material for medicines. In addition, by taking advantage of the high light transmittance and flexible shape, it can be suitably used for elements such as solar cells, flexible circuit substrates, organic EL lighting, and flexible organic EL displays.

[0072] [Flexible Device] Preferred embodiments of the flexible device of the present invention include, but are not limited to, wearable devices, flexible circuits, tactile sensors, batteries, light control films, displays, etc. sealed with the laminate. By adopting this embodiment, the element can have high durability and excellent appearance quality.

[0073] [Solar cell] A preferred embodiment of the solar cell of the present invention is sealed with the laminate. The solar cell is a perovskite solar cell, a dye-sensitized solar cell, a compound solar cell, a tandem structure solar cell, etc., but is not limited to these. By adopting this embodiment, the element can have high durability and high power generation efficiency.

[0074] [Optical sensor] A preferred embodiment of the optical sensor of the present invention is, but is not limited to, an image sensor, a biosensor, an infrared sensor, a microwave sensor, etc., sealed with the laminate. By adopting this embodiment, a sensor having a high element durability and high light receiving efficiency can be obtained. EXAMPLES

[0075] The present invention will be described in detail below with reference to examples, although the present invention is not limited to the following examples.

[0076] [Evaluation method] (1) Thickness of each layer A sample for cross-sectional observation was prepared by FIB method (specifically, based on the method described in "Polymer Surface Processing Science" (by Akira Iwamori) pp. 118-119) using a microsampling system (FB-2000A, Hitachi, Ltd.). The cross-section of the sample for observation was observed with a transmission electron microscope (H-9000UHRII, Hitachi, Ltd.) at an accelerating voltage of 300 kV, and the thicknesses of the A layer and the anchor coat layer of the laminate were measured.

[0077] (2) Composition and thickness of layer A The composition of layer A of the laminate was analyzed by X-ray photoelectron spectroscopy (XPS). From the outermost surface of layer A to a depth of 10 nm, etching and composition analysis were repeated in increments of 5 nm in SiO2 equivalent thickness using argon ion etching, and thereafter, etching and composition analysis were repeated in increments of 8.7 nm in SiO2 equivalent thickness until the atomic concentrations of magnesium, calcium, and zinc were below 1.0 atm%.

[0078] The XPS measurement conditions were as follows. Equipment: PHI5000VersaProbeII (ULVAC-PHI) Excitation X-ray: monochromatic AlKα Analysis range: φ100μm Photoelectron escape angle: 45° Ar ion etching: 3.0kV, raster size 2×2.

[0079] (3) Water vapor permeability (g / m 2 / day) 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 performed using a water vapor transmission rate measuring device (model name: "DELTAPERM" (registered trademark)) manufactured by Technolox, UK, under the following conditions. Two samples were measured per level. The data obtained from the measurements of the two samples were averaged and rounded off to one decimal place to determine the average value for that level, and this value was recorded as the water vapor transmission rate (g / m 2 / day).

[0080] (4) Refractive index of each layer The refractive index of the A layer, anchor coat layer, and substrate was measured using a high-speed spectroscopic ellipsometer M-2000 (JA Woollam). The phase difference Δ and amplitude reflectance Ψ spectrum measured for the laminate were compared with the Δ and Ψ calculated from the calculation model, and the refractive index and film thickness were changed to approach the measured values ​​and fitted to obtain the refractive index. The ellipsometry measurement conditions were as follows: ·Incidence angle: 65°, 70°, 75° ·Measurement wavelength: 245nm~1680nm Analysis software: CompleteEASE Beam diameter: 2mm x 8mm

[0081] (5)Light transmittance The total light transmittance was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7361 (1997).

[0082] Example 1 A polyethylene terephthalate film having a thickness of 50 μm ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) was used as the substrate.

[0083] (Formation of layer A) Using the winding deposition apparatus shown in FIG. 3, an MgO+SiO2 layer was formed as layer A on the substrate surface by electron beam (EB) deposition to a target thickness of 150 nm.

[0084] The specific operation is as follows. First, as the deposition materials, granular magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO2 (purity 99.99%) having a size of about 2 to 5 mm were heated at 100°C for 8 hours in advance. Next, each material (deposition material B: MgO, deposition material C: SiO2) was set in a carbon crucible 12 as shown in Figure 5. The material area ratio of MgO and SiO2 was set to MgO:SiO2 = 2:1. In the winding chamber 5, the surface of the substrate 1 on which the A layer was to be provided was set on the unwinding roll 6 so that it faced the crucible 12, and the substrate was unwound and passed through the main drum 10 via guide rolls 7, 8, and 9. At this time, the temperature of the main drum was controlled to -15°C. Next, the pressure inside the deposition device 4 was reduced by a vacuum pump, and the total pressure was set to 5.0 x 10 -3 Next, oxygen was introduced into the deposition device 4 from the oxygen nozzle 11, and the total pressure was adjusted to 1×10 Pa or less so that the oxidation degree of the M portion of the A layer was 0.83 and the oxidation degree of the A layer interface portion was 0.88. -2 Pa or more 5×10 -1 The pressure was controlled to within a range of 10 Pa or less. Next, one electron gun (hereinafter, EB gun) 14 was used as a heating source to uniformly heat MgO and SiO2. The EB conditions were an acceleration voltage of 30 kV, an applied current of 300 to 2000 mA, and a deposition rate of 50 nm / sec, and an A layer was formed on the surface of the substrate. The thickness of the A layer was adjusted by the applied current and the film transport speed. Then, the film was wound around a winding roll 19 via guide rolls 16, 17, and 18.

[0085] Then, test pieces were cut out from the obtained laminate and various evaluations were carried out. The results are shown in the table.

[0086] Example 2 A laminate was obtained in the same manner as in Example 1, except that a substrate on which an anchor coat layer was formed by the following procedure was used as the substrate. The results are shown in the table.

[0087] (Synthesis of polyurethane compounds having aromatic ring structures) In a 5-liter four-neck flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., product name: Epoxy Ester 3000A) and 710 parts by mass of ethyl acetate were placed and heated to an internal temperature of 60°C. 0.2 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by mass of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise over 1 hour while stirring. After the end of the dropwise addition, the reaction was continued for 2 hours, and then 25 parts by mass of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise over 1 hour. After the dropwise addition, the reaction was continued for 5 hours to obtain a polyurethane compound having an aromatic ring structure with a weight average molecular weight of 20,000.

[0088] (Formation of anchor coat layer) As the substrate, a polyethylene terephthalate film having a thickness of 100 μm or 50 μm ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) was used.

[0089] As a coating liquid for forming an anchor coat layer, 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), 5 parts by mass of 1-hydroxy-cyclohexylphenyl-ketone (manufactured by BASF Japan Ltd., trade name: "IRGACURE" (registered trademark) 184), 3 parts by mass of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-503), 170 parts by mass of ethyl acetate, 350 parts by mass of toluene, and 170 parts by mass of cyclohexanone were mixed to prepare a coating liquid. Next, the coating liquid was applied to the substrate with a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, and after drying, ultraviolet treatment was performed under the following conditions to provide an anchor coat layer with a thickness of 1 μm. UV treatment equipment: LH10-10Q-G (manufactured by 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.

[0090] Example 3 A laminate was obtained in the same manner as in Example 1, except that the direction and flow rate of the oxygen nozzle were changed to control the film formation conditions so that the oxidation degree of the M portion of the A layer was 0.75 and the oxidation degree of the interface portion of the A layer was 0.85. The results are shown in Table 1.

[0091] Example 4 A laminate was obtained in the same manner as in Example 1, except that the direction and flow rate of the oxygen nozzle were changed to control the film formation conditions so that the oxidation degree of the M portion of the A layer was 0.65 and the oxidation degree of the interface portion of the A layer was 0.85. The results are shown in Table 1.

[0092] Example 5 A laminate was obtained in the same manner as in Example 1, except that the direction and flow rate of the oxygen nozzle were changed to control the film formation conditions so that the oxidation degree at the interface of layer A was 0.80. The results are shown in the table.

[0093] Example 6 A laminate was obtained in the same manner as in Example 1, except that the film formation conditions were controlled by changing the direction and flow rate of the oxygen nozzle so that the oxidation degree of the M portion of the A layer was 0.75 and the oxidation degree of the interface portion of the A layer was 0.80. The results are shown in Table 1.

[0094] Example 7 A laminate was obtained in the same manner as in Example 1, except that the direction and flow rate of the oxygen nozzle were changed to control the film formation conditions so that the oxidation degree of the M portion of the A layer was 0.65 and the oxidation degree of the interface portion of the A layer was 0.80. The results are shown in Table 1.

[0095] Example 8 A laminate was obtained in the same manner as in Example 1, except that granular zinc oxide CaO (purity 99.9%) having a size of about 1 to 3 mm and granular silicon oxide SiO (purity 99.9%) having a size of about 2 to 5 mm were used as deposition materials to form a CaO+SiO2 layer as layer A. The results are shown in the table.

[0096] Example 9 A laminate was obtained in the same manner as in Example 1, except that granular zinc oxide ZnO (purity 99.9%) having a size of about 1 to 3 mm and granular silicon oxide SiO (purity 99.9%) having a size of about 2 to 5 mm were used as deposition materials to form a ZnO+SiO2 layer as layer A. The results are shown in the table.

[0097] Comparative Example 1 A laminate was obtained in the same manner as in Example 1, except that the film formation conditions were controlled so that the oxidation degree of the M portion of the A layer was 0.60 and the oxidation degree of the interface portion of the A layer was 0.70 without introducing oxygen gas. The results are shown in Table 1.

[0098] Comparative Example 2 A laminate was obtained in the same manner as in Comparative Example 1, except that granular zirconium dioxide ZrO2 (purity 99.99%) having a size of about 2 to 5 mm was used as the deposition material. The results are shown in the table.

[0099] Comparative Example 3 Except for using granular tin oxide SnO2 (purity 99.99%) having a size of about 1 to 3 mm as the deposition material, a laminate was obtained in the same manner as in Comparative Example 1. The results are shown in the table.

[0100] Comparative Example 4 A laminate was obtained in the same manner as in Comparative Example 1, except that granular magnesium Mg (purity 99.99%) and silicon Si (purity 99.9%) having a size of about 1 to 3 mm were used as deposition materials. The results are shown in Table 1. Note that the degree of oxidation is not recorded because oxygen was not detected.

[0101] [Table 1]

[0102] [Table 2]

[0103] In Examples 1 to 7, the oxidation degree of the M portion of the A layer was in the range of 0.65 to 0.90, the oxidation degree of the interface portion was in the range of 0.80 to 0.90, and the water vapor permeability was 5.0 × 10 -2 (g / m 2 / day) and light transmittance of 88% or more.

[0104] As in Examples 8 and 9, even in the case of different composite oxides (tin oxide and silicon dioxide, calcium oxide and silicon dioxide), the water vapor permeability was 5.0 × 10 -2 (g / m 2 / day) and the light transmittance is good at 87% or more.

[0105] On the other hand, in Comparative Example 1, the degree of oxidation of the M portion and the interface portion is low, and the light transmittance is poor. Comparative Examples 2 and 3 are single materials, and are inferior in gas barrier properties and light transmittance compared to the examples in which two types of deposition materials are mixed. In addition, Comparative Example 4 is inferior in both gas barrier properties and light transmittance due to the color of the elements and the deterioration of the film caused by water vapor. [Industrial Applicability]

[0106] The laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, etc., and can therefore be usefully used as a packaging material for food, medicine, etc. In addition, since it has excellent light transmittance, it can be usefully used as a member for optical electronic devices such as organic EL televisions, solar cells, and optical sensors, but the applications are not limited thereto. [Explanation of symbols]

[0107] 1 Base material 2 A layer 3 Anchor coat layer (layer B) 4. Winding-type electron beam (EB) deposition equipment 5. Winding Room 6 Unwinding roll 7,8,9 Unwinding side guide roll 10 Main Drum 11a, 11b Oxygen gas introduction nozzle 12 Crucible 13 Evaporation materials 14 Electron gun 15 Electron beam 16, 17, 18 Winding side guide roll 19 Winding roll 20 Oxygen gas introduction nozzle 21 Gas inlet 22 Evaporation material B 23 Evaporation material C

Claims

1. A laminate comprising a substrate and a layer A on at least one side thereof, the layer A containing at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table, and oxygen, and an oxidation degree, expressed as follows, of a portion M of the layer A is 0.65 to 0.

90. The M portion of the A layer is a region extending from a portion 5 nm deep from the outermost surface of the A layer to a portion 30 nm deep from the interface reference plane toward the surface. The interface reference plane is the location where the metal element content becomes <1.0% for the first time when X-ray photoelectron spectroscopy (XPS) composition analysis is performed while argon etching is performed from the outermost surface of layer A toward the substrate. When the film composition of the M portion of the A layer is evaluated by X-ray photoelectron spectroscopy, the element ratio of oxygen obtained by analysis is X, and the element ratio of oxygen when it is assumed that the metal elements contained in the M portion of the A layer are complete dioxides is Y, where X / Y is the degree of oxidation.

2. 2. The laminate according to claim 1, wherein the degree of oxidation at the interface in the layer A is 0.80 to 0.

90. The interface portion of the A layer refers to a region extending from the interface reference plane of the A layer to a position 30 nm from the interface reference plane of the A layer toward the surface.

3. 3. The laminate according to claim 1, wherein the difference in refractive index between the substrate and Layer A at light with a wavelength of 587.562 nm is 0.20 or less.

4. 3. The laminate according to claim 1, further comprising a layer B between the substrate and the layer A, the layer A and the layer B being in contact with each other, and a difference in refractive index between the layer A and the layer B at light with a wavelength of 587.562 nm being 0.20 or less.

5. 3. The laminate according to claim 1, wherein the layer A contains one element selected from the group consisting of magnesium (Mg), zinc (Zn), and calcium (Ca), and silicon (Si).

6. 6. The laminate according to claim 5, wherein the A layer contains magnesium (Mg) and silicon (Si), and has a magnesium (Mg) atomic concentration of 5 to 50 atm %, a silicon (Si) atomic concentration of 2 to 30 atm %, and an oxygen (O) atomic concentration of 45 to 70 atm %, as measured by X-ray photoelectron spectroscopy.

7. 6. The laminate according to claim 5, wherein the A layer has a ratio (atm %) of atomic concentrations of magnesium (Mg) atoms to silicon (Si) atoms, Mg / (Mg+Si), of 0.30 to 0.

80.

8. Water vapor permeability is 5.0 x 10 －２ g / m ２ The laminate according to claim 1 or 2, wherein the average particle size is less than 1 / day.

9. 3. The laminate according to claim 1, comprising the substrate, the layer A, and the layer C in this order, the layer A and the layer C being in contact with each other, and a difference in refractive index between the layer A and the layer C at light with a wavelength of 587.562 nm being 0.20 or less.

10. The method for producing a laminate according to claim 1 or 2, further comprising a step of forming the A layer by vacuum deposition, wherein the step comprises a mechanism for introducing oxygen gas during deposition.

11. A flexible device using the laminate according to claim 1 or 2.

12. A solar cell using the laminate according to claim 1 or 2.

13. An optical sensor using the laminate according to claim 1 or 2.

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