JP7543690B2 - LAMINATE, MANUFACTURING METHOD FOR LAMINATE, AND ORGANIC ELEMENT - Google Patents

Description

The present invention relates to a laminate that is used for materials that require high gas barrier properties.

Gas barrier films obtained by forming a vapor-deposited layer of an inorganic substance (including an inorganic oxide) on the surface of a film substrate using a physical vapor deposition method (PVD method) such as vacuum deposition, sputtering or ion plating, or a chemical vapor deposition method (CVD method) such as plasma enhanced chemical vapor deposition, thermal chemical vapor deposition or photochemical vapor deposition, are used as packaging materials for foods, medicines and the like that require the blocking of various gases such as water vapor and oxygen, and as components for electronic devices such as electronic paper and solar cells, and these components are required to have high gas barrier properties with a water vapor transmission rate of 5.0 × 10 ^-3 g/( ^m2 ·24hr·atm) or less.

As one method for achieving high gas barrier properties, a gas barrier film in which organic and inorganic layers are alternately laminated to prevent the occurrence of defects by a hole-filling effect (Patent Document 1) and a gas barrier film in which a ZnO- _SiO2- based film is formed on a film substrate by sputtering using a target mainly composed of ZnO and _SiO2 (Patent Document 2) have been proposed.

JP 2005-324406 A JP 2013-147710 A

However, although it is possible to achieve high barrier properties by alternately laminating organic and inorganic layers in multiple layers as in Patent Document 1, there is a problem that the number of steps required for lamination increases, resulting in high costs. Also, as in Patent Document 2, a laminate forming a gas barrier layer mainly composed of ZnO and _SiO2 has problems such as poor chemical resistance of the gas barrier layer due to poor chemical resistance of ZnO, and poor scratch resistance when the thickness of the gas barrier layer is made thin, making it easy to be scratched during film transport or post-processing.

In view of the background of the conventional technology, the object of the present invention is to provide a laminate that has high gas barrier properties even with a simple structure, and further has excellent chemical resistance and scratch resistance.

In order to solve the above problems, the present invention employs the following means.
(1) A laminate having a layer A containing silicon Si, a metal element M and oxygen O on at least one surface of a substrate, in which the average atomic concentration (atm %) ratio M/(M+Si) of layer A in a 10 nm thickness from the outermost surface thereof measured by X-ray photoelectron spectroscopy is 0 to 0.40.

The present invention provides a laminate that has high gas barrier properties against water vapor and chemical resistance.

FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 2 is a cross-sectional view showing another example of the laminate of the present invention. FIG. 1 is a schematic diagram showing a winding type electron beam deposition apparatus for producing a laminate of the present invention. FIG. 2 is a diagram showing a schematic top view of the arrangement of materials for producing a laminate of the present invention. FIG. 2 is a diagram showing a schematic top view of the arrangement of materials for producing a laminate of the present invention. 2 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Example 1 measured by XPS. 1 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Example 2, measured by XPS. 1 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Example 3 measured by XPS. 1 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Example 4 measured by XPS. 13 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Example 5, measured by XPS. 13 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Example 6 measured by XPS. 1 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in a layer A in Comparative Example 1 measured by XPS. 1 shows an atomic concentration ratio M/(M+Si) profile and an atomic concentration ratio profile of each element in layer A in Comparative Example 2 measured by XPS. FIG. 1 is an explanatory diagram relating to the contents of the present invention.

[Laminate]
A preferred embodiment of the laminate of the present invention is a laminate having an A layer containing silicon Si, a metal element M and oxygen O on at least one surface of a substrate, and an average atomic concentration (atm %) ratio M/(M+Si) of 0 to 0.40 as measured by X-ray photoelectron spectroscopy in a 10 nm thickness region from the outermost surface of the A layer. In the present invention, "above" to "below" indicate that the metal element M is a metal element other than silicon Si.

The metal element M contained in the A layer may be magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, tin, etc. From the viewpoint of gas barrier properties, it is preferable that it is at least one selected from the group consisting of magnesium, calcium, and zinc, and from the viewpoints of vapor deposition properties and optical properties, it is more preferable that it is magnesium.

The A layer contains oxygen, and when evaluated by X-ray photoelectron spectroscopy (XPS), 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 _SiO2 film equivalent thickness. From the viewpoint of transparency, denseness, etc., the oxygen atom content is preferably 20.0 atm% or more, and more preferably 40.0 atm% or more. The outermost surface of the A layer refers to the surface opposite to the surface of the A layer closest to the substrate.

The form of the silicon and metal elements contained in layer A is not limited to oxide, nitride, oxynitride, carbide, etc., but from the viewpoint of forming an amorphous film and gas barrier properties, it is preferable that they are contained as at least one compound selected from the group consisting of oxide, nitride, oxynitride, and carbide, and it is more preferable that they are contained as at least one compound selected from the group consisting of oxide, nitride, and oxynitride. As long as layer A contains silicon, metal elements, and oxygen, it does not matter if it contains other inorganic compounds.

It is particularly preferable that layer A contains magnesium oxide and silicon oxide. By containing magnesium oxide and silicon oxide, a dense composite oxide film can be formed, and the gas barrier properties are improved. As long as it contains magnesium oxide and silicon, it may contain other elements.

The average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface is preferably 0 to 0.40. The thickness of the A layer from the outermost surface refers to the converted thickness of argon ion etching of the SiO ₂ film when evaluated by XPS. When determining the average atomic concentration (atm%) ratio measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface, argon ion etching is performed in increments of 5 nm from the outermost surface to a depth of 10 nm. In other words, the average atomic concentration (atm%) ratio measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface is the average value of the values at thicknesses of 5 nm and 10 nm from the outermost surface. By having the average atomic concentration ratio M/(M+Si) at a thickness of 10 nm from the outermost surface be 0.40 or less, the ratio of Si compounds can be made sufficient, and chemical resistance and scratch resistance can be improved. From the same viewpoint, the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy in a thickness of 10 nm from the outermost surface is more preferably 0 to 0.20, and even more preferably 0 to 0.10. The thickness at which the atomic concentration ratio M/(M+Si) satisfies 0 to 0.40 may be thicker than 10 nm from the surface. When determining the average atomic concentration (atm%) ratio M/(M+Si), if a plurality of metal elements are included, the sum of the average atomic concentrations of the respective metal elements is taken as the average atomic concentration of the metal element M, and the same applies below.

In addition, from the viewpoint of ensuring a sufficient ratio of Si compounds in the outermost surface and improving chemical resistance and scratch resistance, when determining the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface, when the sum of the average atomic concentrations (atm%) of magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, and tin is taken as the average atomic concentration of the metal element M, the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface is preferably 0 to 0.40, more preferably 0 to 0.20, and even more preferably 0 to 0.10.

In addition, from the viewpoint of ensuring a sufficient ratio of Si compounds in the outermost surface and improving chemical resistance and scratch resistance, when determining the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface, when the sum of the average atomic concentrations (atm%) of magnesium, calcium, and zinc is taken as the average atomic concentration of the metal element M, the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface is preferably 0 to 0.40, more preferably 0 to 0.20, and even more preferably 0 to 0.10.

Furthermore, from the viewpoint of ensuring a sufficient ratio of Si compounds in the outermost surface and improving chemical resistance and scratch resistance, when determining the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface, when the sum of the average atomic concentrations (atm%) of magnesium is taken as the average atomic concentration of the metal element M, the average atomic concentration (atm%) ratio M/(M+Si) measured by X-ray photoelectron spectroscopy at a thickness of 10 nm from the outermost surface is preferably 0 to 0.40, more preferably 0 to 0.20, and even more preferably 0 to 0.10.

It is preferable that the A layer of the present invention includes a portion where the atomic concentration (atm%) ratio M/(M+Si) in the thickness direction of the A layer continuously slopes. Continuously sloped means that when the content ratio M/(M+Si) of the metal element M and silicon Si in the A layer is determined by XPS at 10 nm intervals in the depth direction, and the values are a0, a1, a2, a3, ... an (a0 is the value at the measurement point on the outermost surface side of A, and an is the value near the substrate), at least three consecutive points satisfy the following formula:

1.2>a(i+1)/ai>1.0
(wherein i represents an integer of 0 or more and n-1 or less).
Here, the vicinity of the substrate refers to a point where the content ratio of metal elements becomes 1.0 atm % or less for the first time when XPS composition analysis is performed while argon ion etching is performed from the outermost surface of the A layer toward the substrate, and the point is taken as the interface reference surface. When multiple metal elements are present, the interface reference plane is the point where the total atomic concentration of those elements is 1.0 atm% or less. In addition, when the base material side contains the same metal element as the metal element contained in the A layer, the portion where the atomic concentration ratio of the element not present in the A layer exceeds 10 atm % is set as the interface reference. By including a continuously inclined portion, defects can be reduced, and even with a thin A layer, high barrier properties and chemical resistance can be obtained, which improves flexibility. can. From the same viewpoint, when determining the atomic concentration (atm%) ratio M/(M+Si) in the thickness direction of the A layer, the following elements are considered: magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, When the sum of the average atomic concentrations (atm %) of germanium and tin is taken as the average atomic concentration of the metal element M, the atomic concentration (atm %) ratio M/(M+Si) in the thickness direction in the A layer continuously slopes. From the same viewpoint, when determining the atomic concentration (atm %) ratio M/(M+Si) in the thickness direction of the A layer, it is preferable to include a portion where the average atomic concentrations (atm %) of magnesium, calcium, and zinc are included. %) is defined as the average atomic concentration of the metal element M, it is preferable that the A layer includes a portion where the atomic concentration (atm %) ratio M/(M+Si) in the thickness direction thereof continuously slopes. In addition, from the same viewpoint, when calculating the atomic concentration (atm%) ratio M/(M+Si) in the thickness direction in the A layer, the sum of the average atomic concentrations (atm%) of magnesium is calculated as the average atomic concentration of the metal element M. It is preferable that the A layer includes a portion where the atomic concentration (atm %) ratio M/(M+Si) in the thickness direction of the A layer continuously slopes.

It is preferable that the A layer of the present invention is a single layer. By being a single layer, it is possible to obtain a laminate with few defects, high barrier properties, and good chemical resistance even with a simple structure. Here, the layer refers to a part that has a boundary surface that can be distinguished from adjacent parts in the thickness direction and has a finite thickness. They can be distinguished by cross-sectional observation with a transmission electron microscope (TEM). More specifically, when the cross section of the laminate is observed with a TEM, it refers to a part that is distinguished by the presence or absence of a discontinuous boundary surface. Even if the composition changes, if there is no boundary surface between them, it is treated as one layer. In addition, from the viewpoint of obtaining a laminate with few defects, high barrier properties, and good chemical resistance even with a simple structure, it is preferable that the constituent elements in the part 10 nm thick from the outermost surface and the other parts in the A layer are the same. For example, the following method can be used for cross-sectional observation. A sample for cross-sectional observation is prepared by the 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 is observed at 200,000x magnification with a transmission electron microscope (H-9000UHRII, Hitachi, Ltd.) at an accelerating voltage of 300 kV.

Regarding the atomic concentration (atm%) ratio M/(M+Si) in the A layer of the present invention, it is preferable that the atomic concentration ratio M _A near the outermost surface and the atomic concentration ratio M _B near the substrate satisfy the relationship M _A < M _B. The term "near the outermost surface" refers to a location 5 nm from the outermost surface in terms of _SiO2 thickness after argon ion etching when evaluated by XPS. The term "near the substrate" is as described above. By having the atomic concentration ratio M _A near the outermost surface and the atomic concentration ratio M _B near the substrate satisfy the relationship M _A < M _B , both the gas barrier property and the chemical resistance can be improved. From the same viewpoint, when determining the atomic concentration ratio M _A near the outermost surface and the atomic concentration ratio M _B near the substrate for the atomic concentration (atm%) ratio M/(M+Si) in the A layer of the present invention, it is preferable that the relationship M A <M B be satisfied when the sum of the average atomic concentrations (atm%) of magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, and tin is taken as the average atomic concentration of the metal element M. Also, from the same viewpoint, when determining the atomic concentration ratio M _A near the outermost surface and the atomic concentration ratio M _B near the substrate for the atomic concentration (atm%) ratio M/(M+Si) in the A layer of the present invention, it is preferable that the relationship M _{A <} M _B be satisfied when the sum of the average atomic concentrations (atm%) of magnesium, calcium, and zinc is taken as the average atomic concentration of the _metal element M. In addition, with regard to the atomic concentration (atm %) ratio M/(M+Si) in layer A of the present invention, when determining the atomic concentration ratio _MA near the outermost surface and the atomic concentration ratio _MB near the substrate, when the sum of the average atomic concentrations (atm %) of magnesium is taken as the average atomic concentration of the metal element M, it is preferable that the relationship _MA < _MB holds.

The A layer of the present invention preferably has an average lifetime of 0.935 ns or less as measured by the positron beam method (thin film 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 method 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. The method is significantly different from the usual positron annihilation method in that a positron beam is used as a positron source instead of a radioisotope ( ^22Na ), and is a method that enables the measurement of thin films of about several hundred nm thick formed on silicon or quartz substrates. The average pore radius and number concentration of pores can be obtained from the obtained measured values by the nonlinear least squares program POSITRONFIT. The sub-nm order pores and basic skeletons can be obtained by analyzing the average lifetimes of the third and fourth components.

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 performing an analysis 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.

By having an average lifespan of 0.935 ns or less, the A layer is dense and can exhibit high gas barrier properties. From the viewpoint of gas barrier properties, the average lifespan measured by the positron beam method is preferably 0.912 ns or less, and more preferably 0.863 ns or less. In addition, the lower limit of the average lifespan is not particularly limited, but it is preferably 0.542 ns or more. By having an average lifespan of 0.542 ns or more, sufficient flexibility can be achieved.

In order to achieve the average lifetime of 0.935 ns or less of layer A measured by the positron beam method as specified in the present invention, this can be achieved by densely forming a complex oxide film with an appropriate composition ratio on a substrate having an arithmetic mean roughness Ra of 3.0 nm or less. "Densely formed" here refers to a state in which the oxides are mixed at the atomic level to form a dense network.

The average composition in the thickness direction of the A layer of the present invention is preferably a laminate 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%). The average composition in the thickness direction of the A layer refers to the average composition ratio from the outermost surface to the vicinity of the substrate when a composition analysis is performed by XPS while argon ion etching in _SiO2 equivalent thicknesses of 5 nm from the outermost surface of the A layer toward the substrate.

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

With regard to the average composition in the thickness direction of layer A, in order to ensure a sufficient proportion of silicate bonds in layer A and to improve density and exhibit gas barrier properties, it is preferable that the magnesium atom concentration is 5 atm% or more and/or the silicon atom concentration is 30 atm% or less. A silicate bond is a bond between silicon (Si) and metal (M) via oxygen (O), and can be written as Si-O-M.

With regard to the average composition in the thickness direction of layer A, in order to prevent magnesium and silicon from being insufficiently oxidized, which would result in a decrease in light transmittance, it is preferable that the oxygen atomic concentration is 45 atm% or more. In addition, in order to prevent excessive oxygen from being taken in, which would result in an increase in voids and defects, and to exhibit gas barrier properties, it is preferable that the oxygen atomic concentration is 70 atm% or less.

From the above viewpoints, it is more preferable that the average composition in the thickness direction of Layer A of the present invention is such that the magnesium atomic concentration is 8 to 35 (atm%), the silicon atomic concentration is 6 to 25 (atm%), and the oxygen atomic concentration is 50 to 65 (atm%), and even more preferable that the magnesium atomic concentration is 15 to 30 (atm%), the silicon atomic concentration is 8 to 20 (atm%), and the oxygen atomic concentration is 50 to 65 (atm%).

The average composition in the thickness direction of Layer A of the present invention is preferably a laminate in which the atomic concentration (atm%) ratio Mg/(Mg+Si) of magnesium (Mg) atoms to silicon (Si) atoms is 0.30 to 0.75.

For 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 is suppressed. From the same perspective, 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.

[Method of manufacturing A layer]
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 viewpoint of manufacturing cost, environmental load, gas barrier properties, etc., 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.

As a method for forming a structure in which the atomic concentration (atm%) ratio M/(M+Si) in the thickness direction in the A layer continuously grades, preferred examples of the manufacturing method for the laminate in the present invention include a method in which the evaporation materials are arranged in the transport direction of the substrate by a vacuum deposition method, and a method in which multiple sputter electrodes with different composition ratios are arranged in the transport direction of the substrate by a sputtering method. By using this method, an A layer can be formed efficiently and densely.

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 2 to 5 mm are arranged as the deposition materials as shown in FIG. 4. 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 hearth liner 11, and the substrate is unwound and passed through the main drum 10 via guide rolls 7, 8, and 9. Next, the inside of the deposition device 4 is depressurized by a vacuum pump to obtain 5.0×10 ⁻³ Pa or less. The ultimate vacuum is preferably 5.0×10 ⁻³ Pa or less. If the ultimate vacuum is greater than 5.0×10 ⁻³ Pa, residual gas may be taken into the A layer, and the desired film composition and physical properties may not be obtained. The temperature of the main drum 10 is set to −10° C., for example. From the viewpoint of preventing the substrate from being damaged by heat, it is preferably 20° C. or less, more preferably 0° C. or less. Next, one electron gun (hereinafter, EB gun) 13 is used as a heating source, and the EB gun has an acceleration voltage of 10 kV. The acceleration current and the film transport speed are adjusted so that the thickness of the A layer to be formed is about 200 nm, and the A layer is formed on the surface of the substrate 1. Thereafter, the substrate is wound around the winding roll 18 via guide rolls 15, 16, and 17.

[Thickness of layer A]
The thickness of the A layer in the present invention can be obtained by evaluation using XPS. Specifically, argon ion etching is performed from the top surface of the A layer in _SiO2 equivalent thicknesses of 5 nm each toward the substrate, and the thickness of the A layer from the top surface of the A layer is taken as the thickness of the A layer when the first location where the content ratio of the metal element becomes 1.0 atm% or less is taken as the interface reference plane. When multiple metal elements are present, the interface reference plane is taken as the location where the total atomic concentration of the metal elements becomes 1.0 atm% or less. In addition, when the substrate side contains the same metal element as the metal element contained in the A layer, the interface reference plane is taken as the location where the atomic concentration ratio of the element not present in the A layer exceeds 10 atm%.

The thickness of layer A is preferably 20 nm or more, and preferably 500 nm or less. A thickness of 20 nm or more can prevent the generation of areas that are not formed as a layer, which can prevent the gas barrier properties from being lost. Furthermore, a thickness of layer A of 500 nm or less can prevent the layer from easily cracking, and can also improve flex resistance and stretchability. From the above viewpoints, it is more preferable that the thickness of layer A is 30 nm or more and 300 nm or less.

[Substrate]
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.

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 transparency, 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.

The surface of the substrate on which the A layer 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 of these. In addition, a coating layer of an organic or inorganic substance or a mixture of these may be laminated on the side opposite to the side on which the A layer is formed, in order to improve the slipperiness of the substrate when it is wound up and to improve the scratch resistance of the substrate.

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.

[Anchor coat layer]
The laminate of the present invention may have an anchor coat layer. It is preferable that one surface of the anchor coat layer is in contact with the substrate, and the other surface is 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, 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.

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 having a hydroxyl group and an aromatic ring in the molecule, a diol compound, or a diisocyanate compound.

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 type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, or hydroquinone with a (meth)acrylic acid derivative.

Examples of diol compounds 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, and the like can be used. These can be used alone or in combination of two or more.

Examples of diisocyanate compounds 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 such compounds 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. These compounds may be used alone or in combination of two or more.

The ratio of the components 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 the 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. 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.

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 have excellent thermal dimensional stability and surface protection performance are preferred. These may be used in a single composition or in a mixture of two or more components.

The amount 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% by mass, and more preferably in the range of 10 to 80% by mass, out of a total amount of 100% by mass including the polyurethane compound having an aromatic ring structure.

There are no particular limitations on the material of the photopolymerization initiator as long as it can maintain the gas barrier properties and flex resistance of the laminate of the present invention. Examples of photopolymerization initiators that can be suitably used in the present invention include 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl). Examples of such photopolymerization initiators 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)], etc.

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.

The amount 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%.

Examples of organosilicon compounds 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-isocyanatopropyltriethoxysilane.

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.

The amount 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 %.

As the inorganic silicon compound, silica particles are preferred from the viewpoints of surface protection performance and transparency, and the primary particle size of the silica particles is preferably in the range of 1 to 300 nm, and 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.

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 obtained by a transmission electron microscope (TEM).

The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. When the 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 and reproducibility of the gas barrier properties is improved. When the Ra of the surface 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, making it difficult for the vapor deposition film to become dense, and it may be difficult to obtain the effect of improving the gas barrier properties. In addition, cracks due to stress concentration are likely to occur in parts with many unevenness, which may cause a decrease in the repeatability and reproducibility of the gas barrier properties. Therefore, in the present invention, it is preferable to set the Ra of the anchor coat layer to 10 nm or less, and 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.

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 solids 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, or the like. In addition, in the present invention, it is preferable to dilute the coating material containing a polyurethane compound having an aromatic ring structure with an organic solvent from the viewpoint of coating suitability.

Specifically, it is preferable to dilute the coating material to a solids 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 blended into the coating material that forms 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.

Then, it is preferable to dry the coating film after application to remove the diluting solvent. Here, there is no particular restriction on the heat source used for drying, 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, it is preferable to perform the heating at a temperature of 50 to 150°C. In addition, it is preferable to perform the heating treatment for a period of several seconds to 1 hour. Furthermore, the temperature may be constant during the heating treatment, or the temperature may be gradually changed. In addition, the heating 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 heating treatment may be performed in the air or while an inert gas is enclosed.

Next, it is preferable to perform an active energy ray irradiation treatment on the coating film containing the polyurethane compound having an aromatic ring structure after drying to crosslink the coating film and form an anchor coat layer.

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 from the viewpoint of versatility and efficiency, it is preferable to use ultraviolet treatment. As the ultraviolet source, known sources 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, from the viewpoint of curing efficiency, it is preferable to use active energy rays under an inert gas atmosphere such as nitrogen or argon. The ultraviolet treatment may be performed either under atmospheric pressure or under reduced pressure, but from the viewpoint of versatility and production efficiency, it is preferable to perform the ultraviolet treatment under atmospheric pressure in the present invention. Regarding the oxygen concentration during the ultraviolet treatment, from the viewpoint of controlling the degree of crosslinking of the anchor coat layer, the oxygen gas partial pressure is preferably 1.0% or less, and more preferably 0.5% or less. The relative humidity may be arbitrary.

As a source of ultraviolet light, known sources such as high-pressure mercury lamps, metal halide lamps, microwave electrodeless lamps, low-pressure mercury lamps, xenon lamps, etc. can be used.

The cumulative light amount of the ultraviolet irradiation is preferably 0.1 to 1.0 J/ ^cm2 , and more preferably 0.2 to 0.6 J/ ^cm2 . If the cumulative light amount is 0.1 J/ ^cm2 or more, the desired degree of crosslinking of the anchor coat layer can be obtained, which is preferable. Also, if the cumulative light amount is 1.0 J/ ^cm2 or less, damage to the substrate can be reduced, which is preferable.

[Other layers]
On the outermost surface of the laminate of the present invention, that is, on the A layer, an overcoat layer may be formed for the purpose of improving printability and adhesion with an adhesive layer, etc., within a range in which the gas barrier property is not reduced, or a laminated structure may be formed 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. The outermost surface here refers to the surface of the A layer after the A layer is laminated on the substrate.

[Applications of the laminate]
The laminate of the present invention has high gas barrier properties and can be suitably used as a gas barrier film. The laminate of the present invention can also be used in various organic elements. For example, the laminate can be suitably used in organic elements such as solar cells, flexible circuit substrates, organic EL lighting, and flexible organic EL displays. In addition, by taking advantage of the high barrier properties, the laminate can also be suitably used as an exterior material for lithium ion batteries and a packaging material for pharmaceuticals.

[Organic elements]
A preferred embodiment of the organic element of the present invention is an organic element sealed with the laminate described above. This embodiment makes it possible to provide an element with high durability and excellent appearance quality.

The present invention will be specifically described below based on examples. However, the present invention is not limited to the following examples. In the following, Examples 1 and 6 should be read as Reference Examples 1 and 6.

[Evaluation method]
(1) Composition and thickness of A layer The composition of A layer of the laminate was analyzed by X-ray photoelectron spectroscopy (XPS). From the outermost surface of A layer to a depth of 10 nm, etching and composition analysis were repeated in increments of 5 nm in _SiO2 equivalent thickness by argon ion etching, and thereafter, etching and composition analysis were repeated in increments of ₅ nm in SiO2 equivalent thickness until the atomic concentration of the metal element M became 1.0 atm% or less.
The peaks used in the analysis were 2s for magnesium, 2p for silicon, and 1s for oxygen.

The XPS measurement conditions were as follows.
Apparatus: PHI5000VersaProbeII (ULVAC-PHI, Inc.)
・Excitation X-ray: monochromatic AlKα
Analysis range: φ100μm
・Photoelectron escape angle: 45°
Ar ion etching: 2.0 kV, raster size 2 × 2.

(2) Water vapor permeability (g/( ^m2 ·24hr·atm))
The water vapor transmission rate of the laminate was measured using a water vapor transmission rate measuring device (model name: "DELTAPERM" (registered trademark)) manufactured by Technolox, UK, under the conditions of a temperature of 40°C, a humidity ^of 90% RH, and a measurement area of 50 cm2. Two samples were measured per level. The data obtained by measuring the two samples were averaged to two significant digits, and the average value for that level was calculated, and this value was taken as the water vapor transmission rate (g/( ^m2 ·24hr·atm)).

(3) Chemical resistance test 5 mL of an etching solution (iron II chloride: 27% by mass, hydrochloric acid: 10% by mass) was dropped on the surface of layer A of a 100×100 mm laminate in an environment of 25° C., and after 10 minutes, the etching solution was wiped off and the water vapor permeability was measured and evaluated according to the following criteria. Note that samples whose water vapor permeability before the chemical resistance test was unmeasurable (0.5 g/( ^m2 ·24 hr·atm)) or higher) were rated as "not rated."

○: Less than 10 times the water vapor permeability before chemical resistance testing.

×: 10 times or more the water vapor permeability before the chemical resistance test, or the water vapor permeability after the chemical resistance test is unmeasurable (0.5 g/( ^m2 ·24 hr·atm)) or more).

(4) Positron lifetime and pore radius distribution The positron lifetime and pore radius distribution were measured by the positron beam method (thin film positron annihilation lifetime measurement method). The sample to be measured was attached to a 15 mm x 15 mm square Si wafer and degassed in vacuum at room temperature, and then the measurement was performed. The measurement conditions were as follows.
Equipment: Fuji Invac small positron beam generator PALS200A
Positron source: ^22Na -based positron beam Gamma ray detector: _BaF2 scintillator + photomultiplier tube Instrument constant: 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 number: approximately 5,000,000 counts.

The measurement results were analyzed using the nonlinear least squares program POSITRONFIT for three- or four-component analysis.

Example 1
As the substrate, a polyethylene terephthalate film having a thickness of 50 μm ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) was used.
(Formation of Layer A)
Using the winding type deposition apparatus shown in FIG. 3, a MgO+ _SiO bilayer was formed as layer A on the surface of the substrate by electron beam (EB) deposition to a target thickness of 200 nm.

The specific operation is as follows. First, as the deposition material, granular magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO ₂ (purity 99.99%) having a size of about 2 to 5 mm were heated at 100° C. for 8 hours in advance. Then, each material (deposition material B: MgO, deposition material C: SiO ₂ ) was set in a carbon hearth liner 11 as shown in FIG. 4. The material area ratio of MgO to SiO ₂ was set to MgO:SiO ₂ = 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 as to face the hearth liner 11, and the substrate was unwound and passed through the guide rolls 7, 8, and 9 to the main drum 10. 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 to obtain a pressure of 5.0×10 ^-3 Pa or less. Next, MgO and _SiO2 were uniformly heated using one electron gun (hereinafter, EB gun) 13 as a heating source. The EB conditions were set to an acceleration voltage of 10 kV, 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. After that, the film was wound up on a winding roll 18 via guide rolls 15, 16, and 17.

Test pieces were then cut from the resulting laminate and various evaluations were carried out. The results are shown in Tables 1 and 2.

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 Tables 1 and 2.

(Synthesis of Polyurethane Compound Having Aromatic Ring Structure)
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.) was 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.

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

The coating liquid for forming the anchor coat layer was prepared by mixing 150 parts by weight of the polyurethane compound, 20 parts by weight of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: "Light Acrylate" (registered trademark) DPE-6A), 5 parts by weight of 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF Japan, product name: "IRGACURE" (registered trademark) 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicones, product 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 after drying, ultraviolet treatment was performed under the following conditions to provide an anchor coat layer with a thickness of 1 μm.

Ultraviolet treatment equipment: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: _N2 (nitrogen inert box)
Ultraviolet light source: Microwave type electrodeless lamp Accumulated light quantity: 400 mJ/ ^cm2
Sample temperature control: room temperature.

Example 3
A laminate was obtained in the same manner as in Example 2, except that the material area ratio of MgO to _SiO2 was set to MgO: _SiO2 = 3: 1. The results are shown in Tables 1 and 2.

Example 4
A laminate was obtained in the same manner as in Example 2, except that the distance between the hearth liner 11 and the main drum 10 was 1.5 times that of Example 2. The results are shown in Tables 1 and 2.

Example 5
A laminate was obtained in the same manner as in Example 4, except that the EB irradiation to MgO and _SiO2 was performed at a time-sharing ratio of 2:1. The results are shown in Tables 1 and 2.

Example 6
A laminate was obtained in the same manner as in Example 2, except that the deposition materials B and C were arranged as shown in Figure 5 and the material area ratio of MgO to _SiO2 was MgO: _SiO2 = 1:2. The results are shown in Tables 1 and 2.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 2, except that the deposition materials B and C were arranged as shown in Figure 5 and the material area ratio of MgO to _SiO2 was MgO: _SiO2 = 2: 1. The results are shown in Tables 1 and 2.

(Comparative Example 2)
A laminate was obtained in the same manner as in Comparative Example 1, except that the material area ratio of MgO to SiO ₂ was set to MgO:SiO ₂ = 5:1. The results are shown in Tables 1 and 2.

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 2, except that granular magnesium oxide (MgO) (purity 99.9%) having a size of about 2 to 5 mm was used as the deposition material and set in a carbon hearth liner 11 without a partition. The results are shown in Tables 1 and 2.

(Comparative Example 4)
A laminate was obtained in the same manner as in Comparative Example 4, except that granular silicon dioxide SiO ₂ (purity 99.99%) having a size of about 2 to 5 mm was used as the deposition material. The results are shown in Tables 1 and 2.

Examples 1 to 6 have good gas barrier properties and good chemical resistance. Among them, Examples 1, 2, 4, and 6, which have small average composition M/(M+Si) values in the surface 10 nm (large ratio of Si), show little deterioration in water vapor barrier properties due to chemical resistance. This is because the high _SiO2 concentration near the surface provides a layer with excellent chemical resistance.

On the other hand, in Comparative Examples 1, 2, and 4, the Mg ratio is high throughout the A layer, so that the A layer disappears during the chemical resistance test, and the water vapor barrier properties deteriorate. In Comparative Example 4, the Si ratio is high throughout the A layer, so that the chemical resistance is excellent, and although the A layer does not disappear during the chemical resistance test, the density is lacking, so the water vapor barrier properties are not expressed either before or after the chemical resistance test.

The laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, etc., and can be usefully used, for example, as packaging materials for food, medicines, etc., and as components for electronic devices such as flat-screen televisions and solar cells, but its uses are not limited to these.

Reference Signs List 1: Substrate 2: A layer 3: Anchor coat layer 4: Wind-up type electron beam (EB) deposition device 5: Wind-up chamber 6: Unwinding rolls 7, 8, 9: Unwinding side guide roll 10: Main drum 11: Hearth liner 12: Deposition material 13: Electron gun 14: Electron beam 15, 16, 17: Wind-up side guide roll 18: Wind-up roll 19: Deposition material B
20 Evaporation material C

Claims (8)

A laminate having a layer A containing silicon (Si), a metal element (M) and oxygen (O) on at least one surface of a substrate, the metal element M being magnesium (Mg), the layer A being composed of magnesium (Mg), silicon (Si) and oxygen (O), the layer A having a thickness of 20 nm or more, an average atomic concentration (atm %) ratio M/(M+Si) of 0 to 0.40 measured by X-ray photoelectron spectroscopy over a 10 nm thickness from the outermost surface of the layer A, and the layer A having a mean lifetime of 0.935 ns or less measured by a positron beam method . The laminate according to claim 1, which includes a portion where the atomic concentration (atm%) ratio M/(M+Si) in the thickness direction in the A layer continuously slopes. The laminate according to claim 1 or 2, wherein the layer A is a single layer. 4. The laminate according to claim 1, wherein the atomic concentration (atm %) ratio M/(M+Si) in the A layer satisfies the relationship M _A < M _B between the atomic concentration ratio M _A near the outermost surface and the atomic concentration ratio M _B near the substrate. 5. The laminate according to claim 1, wherein the average composition in the thickness direction of the A layer is a magnesium (Mg) atomic concentration of 8 to 30 (atm %), a silicon (Si) atomic concentration of 6 to 25 (atm %), and an oxygen (O) atomic concentration of 50 to 70 (atm %). 6. The laminate according to claim 1, wherein the ratio Mg/(Mg+Si) of atomic concentrations (atm %) of magnesium (Mg) atoms and silicon (Si) atoms in an average composition in a thickness direction of the A layer is 0.30 to 0.80. The method for producing a laminate according to any one of claims 1 to 6 , wherein the method for forming the A layer is a vacuum deposition method. An organic element encapsulated with the laminate according to any one of claims 1 to 6 .

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