Laminate

Abstract

To provide a laminate that has high production efficiency and high gas barrier performance despite a simple constitution.SOLUTION: A laminate has a layer A at least on one side of a substrate, and the layer A fulfills conditions 1 and 2. Condition 1: the layer A contains at least one element selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, and at least one element selected from the group consisting of silicon, stannum, and germanium, and oxygen. Condition 2: a specific relational expression is fulfilled regarding at least any one element of magnesium, calcium, titanium, zirconium, zinc, aluminum included in the layer A. XAinterface / MAinterface>XAwhole / MAwhole, XAinterface, MAinterface: the content ratio of element X (or metal element) in a layer A interface XAwhole, MAwhole: the content ratio of element X (or metal element) in a layer A whole element X: any one of magnesium, calcium, titanium, zirconium, zinc, aluminum.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Gas barrier films, which are 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 pharmaceuticals that require blocking various gases such as water vapor and oxygen, as well as electronic device components such as electronic paper and solar cells. -2 g / m 2 High gas barrier properties of less than 1 / day are required.

[0003] As one method for achieving high gas barrier properties, a gas barrier film has been proposed in which organic and inorganic layers are alternately laminated to form multiple layers, thereby preventing 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 composite oxide film such as a ZnO-SiO2-based film is formed on a film substrate by sputtering using a target whose main components are ZnO and SiO2 (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-324406 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-147710 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although it is possible to achieve high barrier properties by alternately laminating organic and inorganic layers as in Patent Document 1, lamination requires an increased number of steps, resulting in poor production efficiency and high costs. Also, a laminate formed by sputtering a composite oxide as in Patent Document 2 can be produced at a lower cost than Patent Document 1, but due to the nature of the production method, there is a limit to how fast the film formation speed can be increased, making it difficult to reduce production efficiency and costs.

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

[0007] In order to solve the above problems, the present invention employs the following means. (1) A single continuous layer A is provided on at least one side of the substrate; In the layer A, the content ratio of element X selected from magnesium, calcium, titanium, zirconium, zinc, and aluminum, as measured by depth direction analysis using X-ray photoelectron spectroscopy, changes continuously from the interface with the layer A to a main portion of the layer A, The layer A satisfies conditions 1 and 2. Condition 1: The layer A contains one or more elements selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, one or more elements selected from the group consisting of silicon, tin, and germanium, and oxygen. Condition 2: At least one element of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A satisfies the following relational expression. X A界面 / M A界面 >X A全体 / M A全体 X A界面 : Content ratio of element X at the interface of layer A M A界面 : Metal element content ratio at the interface of layer A X A全体 : Content ratio of element X in the entire A layer MA全体 : Content ratio of metal elements in the entire A layer Element X: One of magnesium, calcium, titanium, zirconium, zinc, or aluminum. (2) Water vapor permeability is 5.0 x 10 -2 g / m 2 The laminate according to (1), wherein the aging time is less than / day. (3) The laminate according to (1) or (2), wherein the layer A has a thickness of 300 nm or less. (4) The laminate according to any one of (1) to (3), wherein the layer A contains magnesium and silicon. (5) The laminate according to any one of (1) to (4), which has an anchor coat layer, one surface of which is in contact with the substrate and the other surface of which is in contact with the layer A. (6) The layer A contains magnesium and silicon, and 1.05<(X A界面 / M A界面 ) / (X A全体 / M A全体 )<2.20. (7) 0.60≦X A界面 / M A界面 ≦1.00 and 0.45≦X A全体 / M A全体 The laminate according to any one of (1) to (6), wherein the ratio of the cross-sectional area to the cross-sectional area is ≦0.80. (8) The laminate according to any one of (1) to (7), wherein the magnesium (Mg) atomic concentration at the interface with the layer A is 20 to 60 atm % and the oxygen (O) atomic concentration at the interface with the layer A is 40 to 80 atm % as measured by X-ray photoelectron spectroscopy. (9) The laminate according to any one of (1) to (8), wherein the atomic concentration of magnesium (Mg), silicon (Si), and oxygen (O) measured by X-ray photoelectron spectroscopy is 5 to 50 atm%, 2 to 30 atm%, and 45 to 70 atm%, respectively, throughout the entire layer A. (10) The method for producing a laminate according to any one of (1) to (9), wherein the A layer interface is formed by vacuum deposition, and the A layer other than the A layer interface is formed by vacuum deposition. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a laminate that can be produced with high efficiency and has a high level of gas barrier properties even with a simple structure. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view showing an example of a laminate of the present invention. [Figure 2] 1 is a cross-sectional view showing an example of a laminate of the present invention. [Figure 3] FIG. 1 is a schematic diagram illustrating a take-up electron beam evaporation apparatus for producing a laminate of the present invention. [Figure 4] FIG. 1 is a schematic diagram illustrating a take-up electron beam evaporation apparatus for producing a laminate of the present invention. [Figure 5] FIG. 2 is a diagram showing a schematic top view of the arrangement of materials for producing the laminate of the present invention. [Figure 6] FIG. 2 is a diagram illustrating the film configuration of layer A of the laminate of the present invention. [Figure 7] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 8] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 9] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 10] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 11] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 12] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 13] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 14] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 15] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 16] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 17] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 18] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 19] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 20] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 21] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 22] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 23] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 24] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 25] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 26] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 27] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 28] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 29] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 30] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. [Figure 31] 1 is a graph of atomic concentration and XA / MA in the depth direction of layer A. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below.

[0011] [Laminate] A preferred embodiment of the laminate of the present invention is a laminate having Layer A on at least one side of the substrate, and Layer A satisfies Conditions 1 and 2. Condition 1: The layer A contains one or more elements selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, one or more elements selected from the group consisting of silicon, tin, and germanium, and oxygen. Condition 2: At least one element of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A satisfies the following relational expression. X A界面 / M A界面 >X A全体 / M A全体 X A界面 : Content ratio of element X at the interface of layer A M A界面 : Metal element content ratio at the interface of layer A X A全体 : Content ratio of element X in the entire A layer M A全体 : Content ratio of metal elements in the entire A layer Element X: One of magnesium, calcium, titanium, zirconium, zinc, or aluminum.

[0012] Layer A preferably contains one or more elements selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, and one or more elements selected from the group consisting of silicon, tin, and germanium. From the viewpoints of gas barrier properties and the formation of a complex oxide, it preferably contains at least magnesium and silicon, zinc and silicon, titanium and silicon, zirconium and silicon, or aluminum and silicon. From the viewpoints of vapor deposition properties and optical properties, Layer A more preferably contains magnesium and silicon, zirconium and silicon, or aluminum and silicon. Of these, it is even more preferable for Layer A to contain magnesium oxide and silicon oxide. By containing magnesium oxide and silicon oxide, a particularly dense complex oxide film can be formed, resulting in good gas barrier properties.

[0013] From the viewpoint of gas barrier properties, the following 1 to 4 are more preferable in this order, with 4 being the most preferable.

[0014] 1. When the total content of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A is taken as 100 atm%, the layer A contains a total of 50 atm% or more of one or more elements selected from the group consisting of magnesium, titanium, zirconium, zinc, and aluminum, and contains any one of these elements in the largest amount.

[0015] 2. When the total content of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A is taken as 100 atm%, the layer A contains a total of 50 atm% or more of one or more elements selected from the group consisting of magnesium, zirconium, and aluminum, and contains any one of these elements in the largest amount.

[0016] 3. When the total content of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A is taken as 100 atm%, the layer A contains a total of 50 atm% or more of one or more elements selected from the group consisting of magnesium and zirconium, and contains any one of these elements in the largest amount.

[0017] 4. When the total content of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A is taken as 100 atm%, the layer A contains 50 atm% or more of magnesium, and contains any one of these elements in the largest amount.

[0018] The layer A of the present invention is defined by its composition obtained by depth profile analysis using X-ray photoelectron spectroscopy (XPS). The layer is removed in 5-nm increments from the outermost surface of layer A, measured in terms of the equivalent thickness of an SiO2 film, using argon ion etching to analyze the composition. The outermost surface of layer A refers to the surface opposite to the surface of layer A closest to the substrate. Argon ion etching and analysis are repeated starting from the measurement point where the total content of magnesium, calcium, titanium, zirconium, zinc, and aluminum in layer A is 1 atm% or more out of 100 atm% of all detected elements. The measurement point where the total content of magnesium, calcium, titanium, zirconium, zinc, and aluminum in layer A is 1 atm% or less is defined as the endpoint (hereinafter also referred to as the interface reference plane). The region between the starting point and the endpoint is defined as layer A. For example, even if a layer containing magnesium and another layer containing aluminum are stacked between the starting point and the endpoint, the layer containing magnesium and the layer containing aluminum are collectively referred to as layer A.

[0019] When there are multiple layers determined to be A layers by the above-mentioned XPS, such as a structure of A1 layer / substrate / A2 layer / substrate (both A1 layer and A2 layer are A layers), it is determined whether each layer corresponding to A layers satisfies the above conditions 1 and 2. In this case, if at least one of the layers corresponding to A layers satisfies the above conditions 1 and 2, the laminate is determined to be a laminate having an A layer on at least one side of the substrate, and the A layer satisfies conditions 1 and 2. The same applies to more preferred embodiments.

[0020] Furthermore, in cases where there are two ways to define the starting point and the end point, such as a structure of substrate / Layer A / substrate, if either of the two ways satisfies the above conditions 1 and 2, the laminate is a laminate having Layer A on at least one side of the substrate, and Layer A satisfies conditions 1 and 2. The same applies to more preferred embodiments.

[0021] The form of the elements contained in Layer A is not particularly limited, and may be oxide, nitride, oxynitride, carbide, etc., but from the viewpoint of gas barrier properties, optical properties, etc., it is preferable that they exist in the form of oxide or oxynitride.

[0022] Layer A of the laminate of the present invention may contain other inorganic compounds as long as it contains one or more elements selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, one or more elements selected from the group consisting of silicon, tin, and germanium, and oxygen.

[0023] Layer A contains oxygen when the average content of oxygen atoms at measurement points from the starting point to the end point is 10.0 atm% or more when evaluated by X-ray photoelectron spectroscopy (XPS). From the viewpoints of transparency, density, etc., the content of oxygen atoms is preferably 20.0 atm% or more, and more preferably 40.0 atm% or more.

[0024] It is preferable that at least one element of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A of the laminate of the present invention satisfies the following relational formula. X A界面 / M A界面 >X A全体 / M A全体 X A界面 : Content ratio of element X at the interface of layer A M A界面 : Metal element content ratio at the interface of layer A X A全体 : Content ratio of element X in the entire A layer M A全体 : Content ratio of metal elements in the entire A layer Element X: One of magnesium, calcium, titanium, zirconium, zinc, or aluminum.

[0025] The entire A layer refers to the area from the point 15 nm from the end point to the base point when evaluated by X-ray photoelectron spectroscopy (XPS). The A layer interface refers to the area from the point 15 nm from the end point to the base point, which is 20% of the film thickness of the entire A layer. The area between the base point and the A layer interface is called the main part of A layer.

[0026] The content ratio of element X in the entire A layer refers to the average atomic concentration of element X at all measurement points when argon ion etching is performed in 5-nm increments in SiO2 equivalent thickness from the starting point to a point 15 nm away from the end point (interface reference plane) on the starting point side. Similarly, the content ratio of metal elements in the entire A layer refers to the average sum of atomic concentrations of metal elements at all measurement points when argon ion etching is performed in 5-nm increments in SiO2 equivalent thickness from the starting point to a point 15 nm away from the end point (interface reference plane) on the starting point side. The metal elements referred to here are elements commonly known as metals and semimetals, including magnesium, calcium, titanium, zirconium, zinc, aluminum, silicon, tin, and germanium.

[0027] The content ratio of element X at the interface of layer A refers to the average atomic concentration of element X at the measurement point on the interface of layer A when similarly argon etching is performed. Similarly, the content ratio of a metal element at the interface of layer A refers to the average sum of the atomic concentrations of metal elements at the measurement point on the interface of layer A when similarly argon etching is performed.

[0028] Generally, it is thought that the presence of an abundance of silicon, tin, germanium, etc., which have high covalent bonds, near the interface improves adhesion to the substrate interface and makes layer A denser. However, in this study, when elements X, such as magnesium, calcium, titanium, zirconium, zinc, and aluminum, which have relatively high ionicity, are present in abundance near the interface, that is, X A界面 / M A界面 >X A全体 / M A全体It was found that the barrier properties were dramatically improved by this. It is believed that the abundance of element X, which has a relatively high ionicity, near the interface forms a dense film with a relatively high degree of crystallinity and order.

[0029] From the above viewpoint, it is more preferable that the element contained in the layer A in the greatest amount among magnesium, calcium, titanium, zirconium, zinc, and aluminum in the layer A as a whole satisfies the above relational expression.

[0030] For at least one element of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A, 1.05<(X A界面 / M A界面 ) / (X A全体 / M A全体 )<2.20. A界面 / M A界面 ) / (X A全体 / M A全体 )≦1.05, the effect of improving the film quality of the entire A layer may not be obtained. A界面 / M A界面 ) / (X A全体 / M A全体 ), the film quality at the interface of the A layer and the film quality of the main part of the A layer formed thereon may become discontinuous, which may make it easier for cracks to form. From the viewpoint of barrier properties and vapor deposition properties, 1.05<(X A界面 / M A界面 ) / (X A全体 / M A全体 )<1.70 is more preferable, and 1.10<(X A界面 / M A界面 ) / (X A全体 / M A全体 )<1.40 is more preferred.

[0031] Also, 0.60≦X A界面 / M A界面 ≦1.00 and 0.45≦X A全体 / M A全体 It is preferable that X is ≦0.80. A界面 / M A界面If the value is less than 0.60, the film quality at the interface with layer A may not be improved, and the overall film quality of layer A may not be improved. A全体 / M A全体 If it is less than 0.45, the film quality of the entire A layer may be reduced and the barrier properties may not be exhibited. <X A全体 / M A全体 If X is too dense, the entire A layer may become too dense, which may cause cracks to occur easily. A界面 / M A界面 It is more preferable that X≦1.00. A全体 / M A全体 ≦0.77, and more preferably 0.55≦X A全体 / M A全体 It is more preferable that it is ≦0.75.

[0032] At the interface with the layer A, the magnesium (Mg) atomic concentration measured by X-ray photoelectron spectroscopy is preferably 20 to 60 atm% and the oxygen (O) atomic concentration is 40 to 80 atm%. From the viewpoint of forming a dense film at the interface with the layer A, the magnesium (Mg) atomic concentration is more preferably 20 to 50 atm% and the oxygen (O) atomic concentration is 50 to 70 atm%, and further preferably the magnesium (Mg) atomic concentration is 25 to 40 atm% and the oxygen (O) atomic concentration is 55 to 65 atm%.

[0033] The entire A layer preferably 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. From the viewpoint of film quality and gas barrier properties, the magnesium (Mg) atomic concentration is more preferably 8 to 35 atm%, a silicon (Si) atomic concentration of 6 to 25 atm%, and an oxygen (O) atomic concentration of 50 to 65 atm%. If the magnesium atomic concentration is greater than 50 atm% or the silicon atomic concentration is less than 2 atm%, the reduced proportion of silicon atoms may make the A layer more likely to become a crystalline layer and more susceptible to cracking. If the magnesium atomic concentration is less than 5 atm% or the silicon atomic concentration is greater than 30 atm%, the proportion of silicate bonds in the A layer may decrease, resulting in a decrease in density and failure to exhibit gas barrier properties. If the oxygen atomic concentration is less than 45 atm%, magnesium and silicon will be insufficiently oxidized, which may result in a decrease in light transmittance, whereas if the oxygen atomic concentration is more than 70 atm%, excessive oxygen will be taken in, which may increase voids and defects and result in a decrease in gas barrier properties.

[0034] Layer A of the laminate of the present invention is preferably an amorphous film. Amorphous refers to an irregular structure in which atoms and molecules do not have a long-range, ordered structure like a crystal. A crystalline structure is prone to grain boundaries, which act as water vapor permeation paths, resulting in poor gas barrier properties and increased cracking, so an amorphous film is preferred. Whether a film is amorphous or not can be confirmed by analytical methods such as cross-sectional TEM and X-ray diffraction (XRD). In cross-sectional TEM, amorphous films exhibit uniform contrast and no grain boundaries, whereas crystalline films exhibit grain boundaries according to the crystal structure, such as a microcrystalline state or a columnar structure.

[0035] The laminate of the present invention has a water vapor permeability of 5.0×10 -2 g / m 2 From the viewpoint of use as a high-grade packaging material or in electronic device applications where relatively high gas barrier properties are required, 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 more likely to occur. Therefore, the water vapor permeability of the laminate of the present invention is preferably 1.0×10 -4 g / m 2 It is preferable that the time period is 1 / day or more, where "day" means 24 hours.

[0036] The thickness of Layer A in the present invention can be determined by evaluation using a transmission electron microscope (TEM). The thickness of Layer A is preferably 5 nm or more, more preferably 10 nm or more. If the thickness is thinner than 5 nm, regions that are not formed as a layer may occur, and sufficient gas barrier properties may not be ensured. Furthermore, the thickness of Layer A is preferably 500 nm or less, more preferably 300 nm or less. If the thickness of Layer A is thicker than 500 nm, cracks may easily occur, and bending resistance and stretchability may decrease. From the viewpoint of obtaining a thin film and good barrier properties, the thickness of Layer A is more preferably 50 nm or more and less than 150 nm.

[0037] The method for forming the A layer is not particularly limited, and methods such as sputtering, vacuum evaporation, ion plating, CVD, and atomic layer deposition (ALD) can be used. Among these methods, vacuum evaporation is preferred as it is inexpensive, simple, and can achieve the desired properties. Among the vacuum evaporation methods, electron beam (EB) evaporation is even more preferred from the perspective of evaporating a compound with a relatively high melting point and controlling the film composition of materials with different vapor pressures. Among these, vacuum evaporation or sputtering is preferred for the A layer interface from the perspective of film quality. Using vacuum evaporation or sputtering allows for the formation of inexpensive, dense films. Reactive evaporation may also be performed by introducing oxygen, nitrogen, water vapor, or other reactive gases, or by using ion assistance. Vacuum evaporation may be performed using either a single-wafer or reel-to-reel system. Figure 3 shows an example of a reel-to-reel system.

[0038] [Example of manufacturing method for layer A] An example of a method for forming Layer A using a winding-type evaporation apparatus (Figure 3) is shown. A compound thin film of materials B and C is formed as Layer A on the surface of substrate 1 by electron beam evaporation. First, granular materials B and C, approximately 2-5 mm in size, are placed in crucibles 11 and 24 in a 1:1 ratio as shown in Figure 5. The evaporation materials are not limited to granules; they may also be in the form of rectangular or tablet-shaped compacts. Furthermore, if the evaporation material absorbs moisture, the moisture in the material may be absorbed into Layer A, potentially preventing the desired film composition and physical properties from being obtained. Therefore, it is preferable to dehydrate the material by heating before use. In winding chamber 5, the substrate 1 is placed on unwinding roll 6 so that the surface on which Layer A is to be formed faces crucible 11. The substrate is then unwound, passed through guide rolls 7, 8, and 9, passed through main drum 10, and then through guide rolls 21 and 22, passed through main drum 23. Next, the pressure inside evaporation apparatus 4 is reduced using a vacuum pump, and a pressure of 5.0 × 10 -3 The ultimate vacuum is 5.0×10 Pa or less. -3 The ultimate vacuum is preferably 5.0 x 10 Pa or less. -3 If the pressure is higher than Pa, residual gas may be trapped in the A layer, making it impossible to obtain the desired film composition and physical properties. The temperature of the main drums 10 and 23 is set to, for example, -15°C. 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 referred to as EB gun) 13 and 26 is used as a heating source, and the film composition of the A layer is measured to be X. A界面 / M A界面 >X A全体 / M A全体 The surfaces of materials B and C of the deposition materials 12 and 25 were heated while changing the residence time so as to satisfy the above condition, and deposition was performed. The EB gun was set to an acceleration voltage of 6 kV, an applied current of 50 to 200 mA, and a deposition rate of 1 nm / sec, and an A layer was formed on the surface of the substrate 1 by EB deposition. The thickness of the A layer was adjusted by the film transport speed. The film was then taken up by a take-up roll 18 via guide rolls 15, 16, and 17.

[0039] The composition ratio of Layer A can be measured by X-ray photoelectron spectroscopy (XPS). When using X-ray photoelectron spectroscopy, argon ion etching is performed in 5 nm increments from the starting point to the end point, and the content ratio of each element is measured at all points. The etching rate of argon ion etching is calculated by measuring the film thickness in advance using a transmission electron microscope (TEM) and etching from the outermost surface of Layer A to the substrate interface using argon ion etching.

[0040] [Base material] The substrate used in the present invention is preferably in the form of a film in order to ensure flexibility. The film may be a single-layer film or a film of two or more layers, for example, formed by a co-extrusion method. The type of film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.

[0041] The material of the substrate used in the present invention is not particularly limited, but it is preferable that the substrate be primarily composed of an organic polymer. Examples of organic polymers that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polystyrene, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymers, polyacrylonitrile, polyacetals, and other polymers. Among these, polyethylene terephthalate or amorphous cyclic polyolefins are preferred, due to their excellent transparency, versatility, and mechanical properties. The organic polymer may be either a homopolymer or a copolymer, and a single organic polymer may be used, or multiple organic polymers may be blended.

[0042] The surface of the substrate on which Layer A is formed may be subjected to pretreatment such as corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or treatment to form an anchor coat layer composed of an organic or inorganic substance or a mixture thereof to improve adhesion and smoothness. Furthermore, a coating layer of an organic or inorganic substance or a mixture thereof may be laminated on the side opposite to the side on which Layer A is formed to improve the slipperiness during winding of the substrate and the scratch resistance of the substrate. Furthermore, a film may be laminated on the side opposite to the side on which Layer A is formed to improve the slipperiness during winding of the substrate and the handling.

[0043] 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 100 μm or less.

[0044] [Anchor coat layer] The laminate of the present invention preferably has an anchor coat layer, one side of which is in contact with the substrate and the other side of which is in contact with the Layer A. Furthermore, it is more preferable that the anchor coat layer contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. If defects such as protrusions or scratches exist on the substrate, pinholes or cracks may form in the Layer A laminated on the substrate from the defects, impairing the gas barrier properties and flex resistance. Therefore, it is preferable to provide an anchor coat layer. Furthermore, if the difference in thermal dimensional stability between the substrate and Layer A is large, the gas barrier properties and flex resistance may also be reduced, so it is preferable to provide an anchor coat layer. Furthermore, from the viewpoint of thermal dimensional stability and flex resistance, the anchor coat layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure, and more preferably further contains an ethylenically unsaturated compound, a photopolymerization initiator, an organosilicon compound, and / or an inorganic silicon compound.

[0045] 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.

[0046] Epoxy (meth)acrylates having a hydroxyl group and an aromatic ring in the molecule can be obtained by reacting a diepoxy compound of an aromatic glycol such as bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, resorcinol, or hydroquinone with a (meth)acrylic acid derivative.

[0047] 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, 1,2-cyclohexyl methyl ether, and the like. Examples of usable solvents include cyclohexanedimethanol, 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, and bisphenol A. These can be used alone or in combination of two or more.

[0048] 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 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 xylene diisocyanate and tetramethylxylylene diisocyanate. These can be used alone or in combination of two or more.

[0049] The component ratios of the epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule, the diol compound, and the diisocyanate compound are not particularly limited as long as they are within a range that results in the desired weight-average molecular weight. The weight-average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. A weight-average molecular weight (Mw) of 5,000 to 100,000 is preferred because the resulting cured film has excellent thermal dimensional stability and flex resistance. The weight-average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted into standard polystyrene.

[0050] 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 epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate, and bisphenol S epoxy di(meth)acrylate. Among these, polyfunctional (meth)acrylates are preferred because of their excellent thermal dimensional stability and surface protection performance. These compounds may be used as a single composition or as a mixture of two or more components.

[0051] The content of the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, it is preferably in the range of 5 to 90 mass% and more preferably in the range of 10 to 80 mass% of the total amount including the polyurethane compound having an aromatic ring structure (100 mass%).

[0052] 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-diphenylethan-1-one, 1-hydroxy-cyclohexylphenyl 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-cyclopentadien-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)phenyl-,2-(O-benzoyloxime)].

[0053] Among these, from the viewpoint of curability and surface protection performance, photopolymerization initiators selected from 1-hydroxy-cyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred. These may be used as a single composition or as a mixture of two or more components.

[0054] The content of the photopolymerization initiator is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10 mass % of the total amount of polymerizable components, and more preferably in the range of 0.1 to 5 mass %.

[0055] 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.

[0056] Among these, from the viewpoints of curability and polymerization activity upon irradiation with active energy rays, at least one organosilicon compound selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is preferred. These may be used in a single composition or in a mixture of two or more components.

[0057] The content of the organosilicon compound is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10 mass % of the total amount of polymerizable components, and more preferably in the range of 0.1 to 5 mass %.

[0058] As the inorganic silicon compound, silica particles are preferred from the viewpoints of surface protection performance and transparency, and the primary particle diameter of the silica particles is preferably in the range of 1 to 300 nm, more preferably in the range of 5 to 80 nm. Note that the primary particle diameter here refers to the particle diameter d calculated by applying the specific surface area s calculated by the gas adsorption method to the following formula (1): d=6 / ρs (1) ρ: Density.

[0059] The thickness of the anchor coat layer is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 2,000 nm or less, and even more preferably 500 nm or more and 1,000 nm or less. If the thickness of the anchor coat layer is thinner than 200 nm, the adverse effects of defects such as protrusions and scratches on the substrate may not be suppressed. If the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer decreases, and the unevenness of the surface of Layer A laminated on the anchor coat layer increases. This makes it difficult to achieve a dense vapor-deposited film, which may make it difficult to achieve improved gas barrier properties. The thickness of the anchor coat layer can be measured from cross-sectional images observed using a transmission electron microscope (TEM).

[0060] The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. Setting Ra to 10 nm or less facilitates the formation of a uniform A layer on the anchor coat layer, improving the repeatability and reproducibility of gas barrier properties, which is desirable. If the Ra of the surface of the anchor coat layer exceeds 10 nm, the unevenness of the A layer surface on the anchor coat layer also increases, making it difficult to achieve a dense vapor-deposited film and making it difficult to achieve improved gas barrier properties. Furthermore, cracks are likely to occur due to stress concentration in areas with many unevenness, which may result in a decrease in the repeatability and reproducibility of gas barrier properties. Therefore, in the present invention, the Ra of the anchor coat layer is preferably 10 nm or less, more preferably 5 nm or less. The Ra of the anchor coat layer in the present invention can be measured using an atomic force microscope (AFM) or the like.

[0061] When applying an anchor coat layer to the laminate of the present invention, the preferred means for applying a coating liquid containing a resin that forms the anchor coat layer is to first adjust the solids concentration of a coating material containing a polyurethane compound having an aromatic ring structure onto a substrate so that the thickness after drying is the desired thickness, and then apply the coating material by, for example, reverse coating, gravure coating, rod coating, bar coating, die coating, spray coating, spin coating, etc. In addition, in the present invention, from the viewpoint of coating suitability, it is preferred to dilute the coating material containing a polyurethane compound having an aromatic ring structure with an organic solvent.

[0062] Specifically, it is preferable to dilute the coating material with a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane, or hexane, or an ether solvent such as dibutyl ether, ethyl butyl ether, or tetrahydrofuran to a solids concentration of 10% by mass or less. These solvents may be used alone or in combination. Various additives may also be added to the coating material forming the anchor coat layer as needed. For example, catalysts, antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers, surfactants, leveling agents, antistatic agents, etc. may be used.

[0063] Next, it is preferable to dry the coating film after application to remove the dilution solvent. The heat source used for drying is not particularly limited, and any heat source such as a steam heater, electric heater, or infrared heater can be used. To improve gas barrier properties, the heating temperature is preferably 50 to 150°C. The heat treatment time is preferably several seconds to 1 hour. The temperature may be constant during the heat treatment, or the temperature may be gradually changed. The heat treatment may be performed while adjusting the relative humidity within a range of 20 to 90% RH during the drying treatment. The heat treatment may be performed in the air or while an inert gas is enclosed.

[0064] Next, it is preferable to perform an active energy ray irradiation treatment on the dried coating film containing a polyurethane compound having an aromatic ring structure to crosslink the coating film, thereby forming an anchor coat layer.

[0065] The active energy rays to be applied in such cases are not particularly limited as long as they can cure the anchor coat layer, but ultraviolet treatment is preferred from the perspective of versatility and efficiency. Known sources of ultraviolet light can be used, such as high-pressure mercury lamps, metal halide lamps, microwave electrodeless lamps, low-pressure mercury lamps, and xenon lamps. Furthermore, from the perspective of curing efficiency, active energy rays are preferably used in an inert gas atmosphere such as nitrogen or argon. The ultraviolet treatment can be performed either under atmospheric pressure or under reduced pressure, but from the perspectives of versatility and production efficiency, the present invention prefers ultraviolet treatment under atmospheric pressure. 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 perspective of controlling the degree of crosslinking of the anchor coat layer. Any relative humidity is acceptable.

[0066] As the ultraviolet light source, known sources such as a high-pressure mercury lamp, a metal halide lamp, a microwave electrodeless lamp, a low-pressure mercury lamp, and a xenon lamp can be used.

[0067] 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 it is less than this, damage to the substrate can be reduced, which is preferable.

[0068] [Other layers] An overcoat layer may be formed on the outermost surface of the laminate of the present invention, i.e., on Layer A, to improve scratch resistance, chemical resistance, printability, etc., to the extent that gas barrier properties are not reduced, or a laminate configuration may be formed in which an adhesive layer or film made of an organic polymer compound is laminated for bonding to elements, etc. Also, a low refractive index layer may be formed to improve optical properties. Note that the outermost surface here refers to the surface of Layer A after Layer A has been laminated on the substrate.

[0069] [Applications of laminates] The laminate of the present invention has high gas barrier properties and can therefore be suitably used as a gas barrier film. The laminate of the present invention can also be used in a variety of electronic devices. For example, the laminate can be suitably used in electronic devices such as solar cells, flexible circuit substrates, organic EL lighting, flexible organic EL displays, electronic paper, and thin-film sensors. Taking advantage of the high barrier properties, the laminate can also be suitably used as an exterior material for lithium-ion batteries, packaging materials for pharmaceuticals, and the like. [Example]

[0070] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[0071] [Evaluation method] (1) Thickness of each layer A sample for cross-sectional observation was prepared by FIB using a microsampling system (FB-2000A, manufactured by Hitachi, Ltd.) (specifically, based on the method described in "Polymer Surface Processing Science" (by Akira Iwamori), pp. 118-119). The cross section of the sample for observation was observed using a transmission electron microscope (H-9000UHRII, manufactured by Hitachi, Ltd.) at an accelerating voltage of 300 kV, and the thickness of Layer A of the laminate was measured.

[0072] (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 5-nm increments of SiO2 equivalent thickness using argon ion etching, and thereafter etching and composition analysis were repeated in 5-nm increments of SiO2 equivalent thickness until the atomic concentration of metal element X reached 1.0 atm% or less.

[0073] The peaks used in the analysis are 2s for magnesium and 2p for calcium. 3 / 2 , titanium is 2p 3 / 2 , zirconium is 3d 5 / 2 , zinc is 2p 3 / 2 , silicon is 2p, tin is 3d 5 / 2 , and oxygen was set to 1s.

[0074] 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: 2.0 kV, raster size 2 x 2.

[0075] (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 made under the conditions above using a water vapor transmission rate measuring device (model name: "DELTAPERM" (registered trademark) manufactured by Technolox, UK). Two samples were measured per level. The data obtained from the measurements of the two samples were averaged and rounded to the nearest tenth to determine the average value for that level, and this value was used as the water vapor transmission rate (g / m 2 / day).

[0076] Example 1 A polyethylene terephthalate film ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the substrate.

[0077] (Formation of Layer A) Using the winding type deposition apparatus shown in Figure 3, an MgO+SiO2 layer was formed as layer A on the surface of the substrate by electron beam (EB) deposition with a target thickness of 200 nm.

[0078] The specific procedure is as follows. First, as deposition materials, granular magnesium oxide (MgO) (purity 99.9%) and silicon dioxide (SiO2) (purity 99.99%) with a size of approximately 2 to 5 mm were preheated at 100°C for 8 hours. Next, the respective materials (deposition material B: MgO, deposition material C: SiO2) were placed in carbon crucibles 11 and 24 as shown in Figure 5. The area ratio of MgO to SiO2 was set to MgO:SiO2 = 1:1. In the winding chamber 5, the substrate 1 was set on the unwinding roll 6 so that the side on which Layer A was to be formed faced the crucibles 11 and 24. The substrate was unwound and passed through guide rolls 7, 8, and 9 onto the main drum 10, and then through guide rolls 21 and 22 onto the main drum 23. The temperature of the main drum was controlled at -15°C. Next, the pressure inside the deposition device 4 was reduced using a vacuum pump, and a 5.0 x 10 -3 Pa or less was obtained. Next, using one electron gun (hereinafter referred to as EB gun) 13 as a heating source, heating and deposition were performed by changing the residence time of MgO and SiO2 so that the ratio of MgO to SiO2 in Layer A corresponded to the composition in Part A of Figure 7. For the subsequent Layer A, EB gun 26 was used, and heating and deposition were performed by changing the residence time of MgO and SiO2 so that the ratio of MgO to SiO2 in Layer A corresponded to the composition in Part B of Figure 7. The EB conditions were an acceleration voltage of 10 kV, and Layer A was formed on the surface of the substrate. The thickness of the formed Layer A was adjusted by the applied current and film transport speed. The film was then taken up on take-up roll 18 via guide rolls 15, 16, and 17.

[0079] Subsequently, test pieces were cut out from the resulting laminate and various evaluations were carried out. The results are shown in the table.

[0080] Example 2 (Synthesis of Polyurethane Compounds with Aromatic Ring Structures) A 5-liter, four-neck flask was charged with 300 parts by weight of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., product name: Epoxy Ester 3000A) and 710 parts by weight of ethyl acetate, and the flask was heated to an internal temperature of 60°C. 0.2 parts by weight of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by weight of dicyclohexylmethane-4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. After the completion of the dropwise addition, the reaction was continued for 2 hours, followed by the dropwise addition of 25 parts by weight of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) over 1 hour. The reaction was continued for 5 hours after the dropwise addition, yielding a polyurethane compound having an aromatic ring structure and a weight-average molecular weight of 20,000.

[0081] (Formation of anchor coat layer) A polyethylene terephthalate film ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the substrate.

[0082] The coating liquid for forming the anchor coat layer was prepared by blending 150 parts by weight of the polyurethane compound, 20 parts by weight of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), 5 parts by weight of 1-hydroxy-cyclohexylphenyl ketone (manufactured by BASF Japan Ltd., trade name: "IRGACURE" (registered trademark) 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicones Co., Ltd., trade name: KBM-503), 170 parts by weight of ethyl acetate, 350 parts by weight of toluene, and 170 parts by weight of cyclohexanone. The coating liquid was then applied to the substrate using a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), dried at 100°C for 1 minute, and then subjected to ultraviolet treatment under the following conditions to form a 1 μm thick anchor coat layer. UV treatment equipment: LH10-10Q-G (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.

[0083] (Formation of Layer A) In forming the MgO+SiO2 layer as layer A, a laminate was obtained in the same manner as in Example 1. The results are shown in the table.

[0084] Example 3 In forming the MgO+SiO2 layer as layer A, a laminate was obtained in the same manner as in Example 2, except that the residence time of MgO and SiO2 in the EB gun 13 was changed and heating and deposition were carried out so that the composition of part A would be as shown in Figure 9. The results are shown in the table.

[0085] Example 4 In forming the MgO+SiO2 layer as layer A, a laminate was obtained in the same manner as in Example 2, except that the residence time of MgO and SiO2 in the EB gun 13 was changed and heating and deposition were carried out so that the composition of part A would be as shown in Figure 10. The results are shown in the table.

[0086] Example 5 In forming the MgO+SiO2 layer (layer A), a laminate was obtained in the same manner as in Example 2, except that the residence time of MgO and SiO2 from the EB gun 26 was changed and heating and deposition were carried out so that the composition of part B would be as shown in Figure 11. The results are shown in the table.

[0087] Example 6 In forming the MgO+SiO2 layer (layer A), a laminate was obtained in the same manner as in Example 2, except that the residence time of MgO and SiO2 from the EB gun 26 was changed and heating and deposition were carried out so that the composition of part B would be as shown in Figure 12. The results are shown in the table.

[0088] Example 7 In forming the MgO+SiO2 layer (layer A), a laminate was obtained in the same manner as in Example 2, except that heating and deposition were performed by changing the residence time and applied current of MgO and SiO2 from the EB gun 13 so that the composition and film thickness of part A would be as shown in Figure 13. The results are shown in the table.

[0089] Example 8 In forming the MgO+SiO2 layer (layer A), a laminate was obtained in the same manner as in Example 2, except that heating and deposition were performed by changing the residence time and applied current of MgO and SiO2 from the EB gun 13 so that the composition and film thickness of part A would be as shown in Figure 14. The results are shown in the table.

[0090] Example 9 A laminate was obtained in the same manner as in Example 2, except that in forming the MgO+SiO2 layer as Layer A, the conveying speed was adjusted so that the total thickness of Layer A was 100 nm. The results are shown in the table.

[0091] Example 10 A laminate was obtained in the same manner as in Example 2, except that in forming the MgO+SiO2 layer as Layer A, the conveying speed was adjusted so that the overall thickness of Layer A was 50 nm. The results are shown in the table.

[0092] Example 11 The MgO+SiO2 layer, which is layer A, was formed using the winding evaporation apparatus shown in Figure 4, and the evaporation materials (evaporation material B: MgO, evaporation material C: SiO2) were similarly prepared as described above. Granular magnesium oxide MgO (purity 99.9%) having a size of approximately 2 to 5 mm was placed in carbon crucible 24, and silicon dioxide SiO2 (purity 99.99%) was placed in carbon crucible 28. The distance between carbon crucibles 24 and 28 in Figure 4 was adjusted so that the composition of layer A would be as shown in Figure 17. MgO was heated and evaporated using EB gun 26, and SiO2 was heated and evaporated using EB gun 30. A laminate was obtained in the same manner as in Example 2. The results are shown in Table 1.

[0093] Example 12 A laminate was obtained in the same manner as in Example 11, using the winding evaporation apparatus shown in Figure 4, except that in forming the MgO+SiO2 layer as layer A, the distance between the carbon crucibles 24 and 28 shown in Figure 4 was adjusted so that the composition of layer A would be as shown in Figure 18. The results are shown in the table.

[0094] Example 13 A laminate was obtained in the same manner as in Example 11, using the winding evaporation apparatus shown in Figure 4, except that in forming the MgO+SiO2 layer as layer A, the distance between the carbon crucibles 24 and 28 shown in Figure 4 was adjusted so that the composition of layer A would be as shown in Figure 19. The results are shown in the table.

[0095] Example 14 A laminate was obtained in the same manner as in Example 2, except that in forming Layer A, deposition material B was changed to CaO and deposition was performed so that Layer A had a composition as shown in Figure 20. The results are shown in the table.

[0096] Example 15 A laminate was obtained in the same manner as in Example 2, except that in forming the A layer, the deposition material B was changed to TiO2 and deposition was performed so that the A layer had the composition shown in Figure 21. The results are shown in the table.

[0097] Example 16 A laminate was obtained in the same manner as in Example 2, except that in forming the A layer, the deposition material B was changed to ZrO2 and deposition was performed so that the A layer had the composition shown in Figure 22. The results are shown in the table.

[0098] Example 17 A laminate was obtained in the same manner as in Example 2, except that in forming the A layer, the deposition material C was changed to SnO and deposition was performed so that the A layer had the composition shown in Figure 23. The results are shown in the table.

[0099] Example 18 A laminate was obtained in the same manner as in Example 2, except that in forming the A layer, the deposition material B was changed to ZnO and deposition was performed so that the A layer had the composition shown in Figure 24. The results are shown in the table.

[0100] (Comparative Example 1) A laminate was obtained in the same manner as in Example 1, except that in forming layer A, MgO and SiO2 were heated and evaporated using only EB gun 26, not EB gun 13, so that the composition of layer A would be as shown in Figure 25. The results are shown in the table.

[0101] (Comparative Example 2) In forming the A layer, MgO and SiO2 were heated and evaporated using only the EB gun 26, not the EB gun 13, so that the composition of the A layer would be as shown in Figure 26, and the conveying speed was adjusted so that the overall film thickness of the A layer would be 100 nm. A laminate was obtained in the same manner as in Example 1. The results are shown in the table.

[0102] (Comparative Example 3) A laminate was obtained in the same manner as in Comparative Example 2, except that in forming Layer A, the conveying speed was adjusted so that the film thickness of the entire Layer A was 50 nm. The results are shown in the table.

[0103] Comparative Example 4 In forming layer A, a laminate was obtained in the same manner as in Example 2, except that the residence time of MgO and SiO2 in the EB gun 13 was changed and heating and deposition were performed so that the composition of part A would be as shown in Figure 28. The results are shown in the table.

[0104] (Comparative Example 5) A laminate was obtained in the same manner as in Comparative Example 4, except that in forming the A layer, only SiO2 was placed in the crucible 24 and deposition was carried out using only the EB gun 26, not the EB gun 13. The results are shown in the table.

[0105] (Comparative Example 6) In forming layer A, MgO and SiO2 were heated and evaporated using only EB gun 26, not EB gun 13, so that the composition of layer A would be as shown in Figure 29, and evaporation material B was changed to TiO2, but other than that, a laminate was obtained in the same manner as in Example 2. The results are shown in the table.

[0106] (Comparative Example 7) A laminate was obtained in the same manner as in Comparative Example 6, except that in forming Layer A, the deposition material B was changed to ZrO2. The results are shown in the table.

[0107] (Comparative Example 8) A laminate was obtained in the same manner as in Comparative Example 6, except that in forming Layer A, the deposition material C was changed to SnO. The results are shown in the table.

[0108] [Table 1]

[0109] [Table 2] [Industrial Applicability]

[0110] The laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, and the like, and can therefore be usefully used, for example, as packaging materials for foods, medicines, and the like, and as components for electronic devices such as organic EL televisions and solar cells, but the uses are not limited to these. [Explanation of symbols]

[0111] 1 Base material 2 A layer 3 Anchor coat layer 4. Wind-up electron beam (EB) deposition equipment 5. Winding Room 6 Unwinding roll 7, 8, 9 Unwinding side guide roll 10,23 Main drum 11,24,28 Crucible 12,25,29 Vapor deposition materials 13,26,30 Electron gun 14,27,31 Electron beam 15, 16, 17 Winding side guide roll 18 Take-up roll 19 Evaporation material B 20 Evaporation material C 21,22 Guide Roll

Claims

1. A single continuous A layer is provided on at least one side of the substrate; In the layer A, a content ratio of an element X selected from magnesium, calcium, titanium, zirconium, zinc, and aluminum, as measured by depth direction analysis using X-ray photoelectron spectroscopy, changes continuously from the interface with the layer A to a main portion of the layer A, The layer A satisfies conditions 1 and 2. Condition 1: The A layer contains one or more elements selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, one or more elements selected from the group consisting of silicon, tin, and germanium, and oxygen. Condition 2: At least one element of magnesium, calcium, titanium, zirconium, zinc, and aluminum contained in the layer A satisfies the following relational expression: X Ａ界面 / M Ａ界面 >X Ａ全体 / M Ａ全体 X Ａ界面 : Content ratio of element X at the interface of layer A M Ａ界面 : Content ratio of metal element at the interface of layer A X Ａ全体 : Content ratio of element X in the entire A layer M Ａ全体 : Content ratio of metal element in the entire A layer Element X: one of magnesium, calcium, titanium, zirconium, zinc, and aluminum.

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

3. The laminate according to claim 1 or 2, wherein the layer A has a film thickness of 300 nm or less.

4. 4. The laminate according to claim 1, wherein the A layer contains magnesium and silicon.

5. 5. The laminate according to claim 1, further comprising an anchor coat layer, one surface of which is in contact with the substrate and the other surface of which is in contact with the A layer.

6. The layer A contains magnesium and silicon, and 1.05<(X Ａ界面 / M Ａ界面 ) / (X Ａ全体 / M Ａ全体 6. The laminate according to claim 4 or 5, wherein the tensile strength is 1.00 or less, and the tensile strength is 1.00 or less.

7. 0.60≦X Ａ界面 / M Ａ界面 ≦1.00, and 0.45≦X Ａ全体 / M Ａ全体 7. The laminate according to claim 1, wherein the value is ≦0.

80.

8. 8. The laminate according to claim 1, wherein the magnesium (Mg) atomic concentration at the interface with the layer A is 20 to 60 atm % and the oxygen (O) atomic concentration at the interface with the layer A is 40 to 80 atm % as measured by X-ray photoelectron spectroscopy.

9. 9. The laminate according to claim 1, wherein the entire layer A 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.

10. The method for producing a laminate according to any one of claims 1 to 9, wherein the A layer interface is formed by a vacuum deposition method, and the A layer other than the A layer interface is formed by a vacuum deposition method.

Images