JP2021169183A - Laminate, method for producing laminate, and organic element - Google Patents

Abstract

To provide a laminate that has high-level gas barrier properties despite its simple structure and also has excellent chemical resistance and excoriation resistance.SOLUTION: A laminate has, on at least one side of a base material, A layer containing silicon Si, a metal element M and oxygen O. In the laminate, an area of 10 nm in thickness from the outermost surface of the A layer has a ratio of average atomic levels (atm%) of M/(M+Si) of 0-0.40.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate used for a material or the like that requires high gas barrier properties.

Physical vapor deposition (PVD method) such as vacuum deposition, sputtering, ion plating, or plasma chemical vapor deposition, thermochemical vapor deposition, photochemical vapor deposition on the surface of the film substrate. A gas barrier film formed by forming a vapor deposition layer of inorganic substances (including inorganic oxides) using a chemical vapor deposition method (CVD method), etc., requires blocking of various gases such as water vapor and oxygen. packaging materials and electronic paper, such as foods and pharmaceuticals and has been used as an electronic device member such as a solar cell, in their members, in water vapor permeability ^{5.0 × 10 -3 g / (m} 2 · 24hr · Atm) or less high gas barrier property is required.

As one of the methods for satisfying high gas barrier properties, gas barrier films (Patent Document 1) in which defects are prevented from occurring due to the fill-in-the-blank effect by alternately laminating organic layers and inorganic layers, and ZnO and SiO ₂ are mainly used. A gas barrier film (Patent Document 2) in _{which a ZnO—SiO 2} system film is formed on a film substrate by sputtering using a target as a component has been proposed.

Japanese Unexamined Patent Publication No. 2005-324406 Japanese Unexamined Patent Publication No. 2013-147710

However, although it is possible to exhibit high barrier properties by alternately laminating organic layers and inorganic layers as in Patent Document 1, there is a problem that the number of steps is increased and the cost is high due to the laminating. was there. _{Further, in the laminate forming the gas barrier layer containing ZnO and SiO 2} as main components as in Patent Document 2, ZnO has poor chemical resistance, the gas barrier layer has poor chemical resistance, and the film thickness of the gas barrier layer is increased. If it is made thinner, the scratch resistance becomes poor, and there is a problem that it is easily scratched during film transportation and post-processing.

An object of the present invention is to provide a laminate having a high degree of gas barrier property even with a simple structure and also having excellent chemical resistance and scratch resistance in view of the background of the prior art.

The present invention employs the following means in order to solve such a problem. That is, it is as follows.
(1) An average atomic concentration (atm%) measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface of the layer A having a layer A containing silicon Si, a metal element M and oxygen O on at least one surface of the base material. ) Laminated body having a ratio M / (M + Si) of 0 to 0.40.

According to the present invention, it is possible to provide a laminate having a high gas barrier property against water vapor and chemical resistance.

It is sectional drawing which showed an example of the laminated body of this invention. It is sectional drawing which showed another example of the laminated body of this invention. It is the schematic which shows typically the winding type electron beam vapor deposition apparatus for manufacturing the laminated body of this invention. It is a figure which shows typically the material arrangement for manufacturing the laminated body of this invention from the upper part. It is a figure which shows typically the material arrangement for manufacturing the laminated body of this invention from the upper part. The atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Example 1 measured by XPS. It is the atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Example 2 measured by XPS. It is the atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Example 3 measured by XPS. It is the atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Example 4 measured by XPS. The atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Example 5 measured by XPS. The atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Example 6 measured by XPS. It is the atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Comparative Example 1 measured by XPS. It is the atomic concentration ratio M / (M + Si) profile of the A layer and the atomic concentration ratio profile of each element in Comparative Example 2 measured by XPS. It is explanatory drawing about the content of this invention.

[Laminate]
A preferred embodiment of the laminate of the present invention has an A layer containing silicon Si, a metal element M and oxygen O on at least one surface of the base material, and is measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface of the A layer. It is a laminate in which the average atomic concentration (atm%) ratio M / (M + Si) is 0 to 0.40. In the present invention, ~ indicates the following, and the metal element M is a metal element other than silicon Si.

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

_{The fact that layer A contains oxygen is the equivalent thickness of the SiO 2} film when evaluated by X-ray photoelectron spectroscopy (XPS), where the layer was removed from the outermost surface of layer A by 5 nm argon ion etching. It means that the content ratio of oxygen atoms is 10.0 atm% or more. From the viewpoint of transparency and density, the oxygen atom content ratio 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 where the A layer is closest to the base material.

The morphology of silicon and metal elements contained in layer A is not limited to oxides, nitrides, nitride nitrides, carbides, etc., but from the viewpoint of forming an amorphous film and gas barrier properties, oxides and nitrides , Preferably contained as at least one compound selected from the group consisting of oxides, nitrides and carbides, and contained as at least one compound selected from the group consisting of oxides, nitrides and nitrides. Is more preferable. As long as the layer A contains silicon, a metal element, and oxygen, other inorganic compounds may be contained.

Above all, it is more preferable that the A layer 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 property is improved. Other elements may be contained as long as magnesium oxide and silicon are contained.

The average atomic concentration (atm%) ratio M / (M + Si) measured by X-ray photoelectron spectroscopy having 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 equivalent thickness of the 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 having a thickness of 10 nm from the outermost surface, argon ion etching is performed at a depth of 10 nm from the outermost surface by 5 nm. That is, the average atomic concentration (atm%) ratio measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface is an average value of values having a thickness of 5 nm and 10 nm from the outermost surface. When the average atomic concentration ratio M / (M + Si) having a thickness of 10 nm from the outermost surface is 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 having a thickness of 10 nm from the outermost surface is more preferably 0 to 0.20, still more preferably 0 to 0.10. Is. 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 layer. When calculating the average atomic concentration (atm%) ratio M / (M + Si), when a plurality of metal elements are contained, the sum of the average atomic concentrations of each metal element is taken as the average atomic concentration of the metal element M, and the same applies hereinafter. ..

Further, from the viewpoint of improving the chemical resistance and scratch resistance by making the ratio of the Si compound on the outermost surface sufficient, the average atomic concentration (atm%) ratio measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface. In determining M / (M + Si), the sum of the average atomic concentrations (atm%) of magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, and tin is the sum of the metal element M. When the average atomic concentration is taken, the average atomic concentration (atm%) ratio M / (M + Si) measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface is preferably 0 to 0.40, preferably 0 to 0. It is more preferably .20 and even more preferably 0 to 0.10.

In addition, the average atomic concentration (atm%) measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface from the viewpoint of improving the chemical resistance and scratch resistance by making the ratio of the Si compound on the outermost surface sufficient. In determining the ratio M / (M + Si), 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, X-ray photoelectron spectroscopy with a thickness of 10 nm from the outermost surface is used. The measured average atomic concentration (atm%) ratio M / (M + Si) is preferably 0 to 0.40, more preferably 0 to 0.20, and further preferably 0 to 0.10. preferable.

Further, from the viewpoint of improving the chemical resistance and scratch resistance by making the ratio of the Si compound on the outermost surface sufficient, the average atomic concentration (atm%) ratio measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface. In determining M / (M + Si), 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 measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface. The (atm%) ratio M / (M + Si) is preferably 0 to 0.40, more preferably 0 to 0.20, and even more preferably 0 to 0.10.

It is preferable to include a portion in the layer A of the present invention in which the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction is continuously inclined. In the A layer, the continuous inclination means that the content ratio M / (M + Si) of the metal element M and silicon Si in the layer A is determined at 10 nm intervals in the depth direction, and the values are a0, a1, a2, a3 ... When an (a0 is a value at the measurement point on the outermost surface side of A and an is a value near the base material), it means that at least three consecutive points satisfy the following formula.

1.2> a (i + 1) / ai> 1.0
(In the formula, i represents an integer of 0 or more and n-1 or less)
Here, the vicinity of the base material is defined as the interface reference surface where the metal element content ratio becomes 1.0 atm% or less for the first time after performing XPS composition analysis while performing argon ion etching from the outermost surface of the A layer toward the base material. When this is done, the portion 30 nm from the interface reference plane to the outermost surface side of the A layer is referred to. When a plurality of metal elements are present, the interface reference plane is a portion where the total atomic concentration thereof is 1.0 atm% or less. When the base material contains a metal element similar to the metal element contained in the A layer, the interface reference plane is a portion where the atomic concentration ratio of the element not present in the A layer exceeds 10 atm%. do. Defects can be reduced by including continuously inclined portions, and high barrier properties and chemical resistance can be obtained even with a thin A layer thickness, so that flexibility can be improved. From the same viewpoint, in determining the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction in the layer A, magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, etc. 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 layer A is continuously inclined. It is preferable to include a portion to be used. Further, from the same viewpoint, in obtaining the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction in the layer A, the sum of the average atomic concentrations (atm%) of magnesium, calcium, and zinc is taken as the metal element M. It is preferable to include a portion in the layer A in which the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction is continuously inclined when the average atomic concentration of is taken. In addition, from the same viewpoint, when determining the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction in the layer A, 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 to include a portion in the A layer in which the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction is continuously inclined.

The layer A of the present invention is preferably a single layer. Since it is a single layer, it is possible to obtain a laminate having few defects, high barrier properties, and good chemical resistance even with a simple structure. Here, the layer refers to a portion having a boundary surface distinguishable from the adjacent portion and having a finite thickness in the thickness direction. They can be distinguished by cross-section observation with a transmission electron microscope (TEM). More specifically, when the cross section of the laminated body is observed by TEM, it is distinguished by the presence or absence of a discontinuous boundary surface. Even if the composition is changed, if there is no above-mentioned boundary surface between them, it is treated as one layer. Further, from the viewpoint of obtaining a laminate having few defects, high barrier properties, and good chemical resistance even with a simple structure, the constituent elements are the same in the portion having a thickness of 10 nm from the outermost surface and the portion other than that in the A layer. It is preferable to have. For example, the cross-section observation can be performed by the following method. A sample for cross-section observation is described by the FIB method using a microsampling system (FB-2000A manufactured by Hitachi, Ltd.) (specifically, "Polymer Surface Processing" (written by Akira Iwamori), pp. 118-119. (Based on the method of). The cross section of the observation sample is observed with a transmission electron microscope (H-9000UHRII manufactured by Hitachi, Ltd.) at an acceleration voltage of 300 kV at a magnification of 200,000.

The atomic concentration of the layer A of the present invention (atm%) Ratio M / (M + Si), the atomic concentration ratio _{M B} near atomic concentration ratio _{M A} and the substrate in the vicinity of the outermost surface is the relation of _M A _{<M B} Is preferable. The vicinity of the outermost surface means a portion of 5 nm from the outermost surface in _{the SiO 2 equivalent thickness of argon ion etching when evaluated by XPS.} Further, the vicinity of the base material is as described above. By atomic concentration ratio M _B near atomic concentration ratio M _A and the substrate in the vicinity of the outermost surface is M _{A <M B,} it can be made better than both the gas barrier properties and chemical resistance. From the same viewpoint, the atomic concentration of the layer A of the present invention (atm%) Ratio M / (M + Si), Upon obtaining the atomic concentration ratio M _A and the atomic concentration ratio M _B near the substrate in the vicinity of the outermost surface, magnesium , calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, and the sum of the average atomic concentration of tin (atm%) when the average atomic concentration of the metal element M, M _a <it is preferable that a relationship of _{M B.} From the same viewpoint, the atomic concentration of the layer A of the present invention (atm%) Ratio M / (M + Si), Upon obtaining the atomic concentration ratio M _A and the atomic concentration ratio M _B near the substrate in the vicinity of the outermost surface , magnesium, calcium, and the sum of the average atomic concentration of zinc (atm%) when the average atomic concentration of the metal element M, it is preferable that a relationship of M a _{<M B.} In addition, the atomic concentration of the layer A of the present invention (atm%) Ratio M / (M + Si), Upon obtaining the atomic concentration ratio M _A and the atomic concentration ratio M _B near the substrate in the vicinity of the outermost surface, the average of the magnesium the sum of atomic concentration (atm%) when the average atomic concentration of the metal element M, it is preferable that a relationship of M a _{<M B.}

The A layer of the present invention has an average lifetime of 0 as measured by the positron beam method (measurement of positron annihilation lifetime for thin films) (see "Science of positron measurement" (Japan Radioisotope Association), Chapter I, Section 1, Section V, Section 2). It is preferably .935 ns or less. The positron beam method is one of the methods for measuring the positron annihilation lifetime, and measures the time (several hundred ps to several tens of ns order) from when a positron is incident on a sample until it disappears. This is a non-destructive evaluation method for information on the size, number concentration, and size distribution of pores of 1 to 10 nm. ^{The point that a positron beam is used instead of a radioisotope (22} Na) as a positron radiation source is significantly different from the usual positron annihilation method, and it is possible to measure a thin film with a thickness of several hundred nm formed on a silicon or quartz substrate. This is a possible method. From the obtained measured values, the average pore radius and the number concentration of pores can be obtained by the nonlinear least squares program POSITRONFIT. Those corresponding to sub-nm order pores and basic skeletons can be obtained by analyzing the average lifetimes of the third component and the fourth component.

Here, the third component means the average life obtained by selecting the analysis for the three components as the measurement condition of the average life by the positron beam method, and the fourth component means the measurement of the average life by the positron beam method. It refers to the average life obtained by selecting the analysis for 4 components as a condition. When the analysis is performed by POSITRONFIT, the number of components of POSITRONFIT is determined from the number of peaks obtained by the pore radius distribution curve calculated by using the distribution analysis program CONTIN based on the inverse Laplace transform method. It is judged that the analysis is valid when the average pore radius calculated from POSITRONFIT and the peak position of the pore radius distribution curve of CONTIN match. The average life of the third component as used in the present invention refers to the average life of the third component.

When the average life is 0.935 ns or less, the layer A is dense and high gas barrier properties can be exhibited. From the viewpoint of gas barrier property, the average lifetime measured by the positron beam method is preferably 0.912 ns or less, more preferably 0.863 ns or less. The lower limit of the average life is not particularly limited, but is preferably 0.542 ns or more. When the average life is 0.542 ns or more, the flexibility can be made sufficient.

In order for the average lifetime measured by the positron beam method of layer A specified in the present invention to be 0.935 ns or less, for example, a composite oxide film is placed on a substrate having an arithmetic mean roughness Ra of 3.0 nm or less. Is achieved by densely forming with a suitable composition ratio. The term "densely formed" as used herein means a state in which each oxide is mixed at the atomic level to form a dense network.

Regarding the average composition of the A layer of the present invention in the thickness direction, the magnesium (Mg) atomic concentration is 5 to 50 (atm%), the silicon (Si) atomic concentration is 2 to 30 (atm%), and the oxygen (O) atomic concentration is It is preferably a laminate of 45 to 70 (atm%). The average composition of the A layer in the thickness direction is the composition ratio from the outermost surface to the vicinity of the base material when the composition is analyzed by argon ion etching _{from the outermost surface of the A layer to the base material by 5 nm in terms of SiO 2 equivalent thickness.} Is the average of.

Regarding the average composition of the A layer in the thickness direction, it is preferable that the magnesium atom concentration is 50 atm% or less and / or the silicon atom concentration is 2 atm% or more from the viewpoint of suppressing the formation of a crystal layer and the tendency for cracks to occur.

Regarding the average composition in the thickness direction of the A layer, the magnesium atom concentration is 5 atm% or more, and / or the silicon atom from the viewpoint of making the ratio of silicate bonds in the A layer sufficient, improving the denseness and exhibiting the gas barrier property. The concentration is preferably 30 atm% or less. The silicate bond is a bond between silicon (Si) and a metal (M) via oxygen (O), and can be described as Si—OM.

Regarding the average composition of the layer A in the thickness direction, the oxygen atom concentration is preferably 45 atm% or more from the viewpoint of suppressing the decrease in light transmittance due to insufficient oxidation of magnesium and silicon. Further, it is preferable that the oxygen atom concentration is 70 atm% or less from the viewpoint of suppressing excessive intake of oxygen and increasing voids and defects and exhibiting gas barrier properties.

From the above viewpoint, regarding the average composition of the A layer of the present invention in the thickness direction, the magnesium atom concentration is 8 to 35 (atm%), the silicon atom concentration is 6 to 25 (atm%), and the oxygen atom concentration is 50 to 65 (atm%). %), More preferably, the magnesium atom concentration is 15 to 30 (atm%), the silicon atom concentration is 8 to 20 (atm%), and the oxygen atom concentration is 50 to 65 (atm%). ..

Regarding the average composition of the A layer of the present invention in the thickness direction, a laminated body in which the atomic concentration (atm%) ratio Mg / (Mg + Si) of magnesium (Mg) atom and silicon (Si) atom is 0.30 to 0.75. It is preferable to have.

Regarding the average composition in the thickness direction of the A layer, the atomic concentration (atm%) ratio is Mg / (Mg + Si) ≥ 0.30, so that the ratio of silicate bonds in the A layer is sufficient and the density is improved. It can be improved to develop gas barrier properties. When the atomic concentration (atm%) ratio is Mg / (Mg + Si) ≦ 0.70, it is possible to suppress the presence of a crystal portion in the A layer and prevent cracks from easily forming. From the same viewpoint, the atomic concentration (atm%) ratio Mg / (Mg + Si) is more preferably 0.35 to 0.70, and even more preferably 0.40 to 0.65.

[Manufacturing method of layer A]
The method for forming the A layer is not particularly limited, and is 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, and a large method. A pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method and the like can be used. From the viewpoint of manufacturing cost, environmental load, gas barrier property, etc., it is preferable to use the vacuum deposition method. From the viewpoint of compound vapor deposition, it is more preferable to use electron beam (EB) vapor deposition and ion beam assisted vapor deposition (IBAD) among the vacuum vapor 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 layer A is continuously inclined, as a method for producing a laminate in the present invention, an evaporative material is arranged by a vacuum vapor deposition method. A method of arranging a plurality of materials in the transport direction of the base material and a method of arranging a plurality of sputter electrodes having different composition ratios in the transport direction of the base material by a sputtering method can be preferably mentioned. By adopting this method, it is possible to efficiently and densely form the A layer.

An example of the method of forming the A layer by the take-up type vapor deposition apparatus (FIG. 3) when the vacuum vapor deposition method is used is shown. A compound thin film of materials B and C is provided as a layer A on the surface of the base material 1 by an electron beam (EB) vapor deposition method. First, as the vapor deposition material, granular material B and material C having a size of about 2 to 5 mm are arranged as shown in FIG. The vapor deposition material is not limited to granules, and a molded product such as a square or tablet may be used. Further, as the arrangement of the vapor deposition source material, the arrangement ratio of the material B and the material C or the material in which the two materials are mixed in advance may be used so that the layer A has a desired film structure. Further, if the vapor-deposited material absorbs moisture, moisture in the material may be taken into the layer A, and the desired film composition and physical properties may not be obtained. Therefore, the material is dehydrated by heating before use. Is preferable. In the take-up chamber 5, the unwinding roll 6 is set so that the surface of the base material 1 on which the A layer is provided faces the hearth liner 11, and the unwinding roll is unwound via the guide rolls 7, 8 and 9. , Pass through the main drum 10. Next, the inside of the vapor deposition apparatus 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 degree is ^{larger 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. as an example. From the viewpoint of preventing heat loss of the base material, the temperature is preferably 20 ° C. or lower, more preferably 0 ° C. or lower. Next, one electron gun (hereinafter referred to as EB gun) 13 is used as a heating source, the acceleration voltage of the EB gun is 10 kV, and the acceleration current and the film transfer speed are adjusted so that the thickness of the A layer to be formed is about 200 nm. It is adjusted to form a layer A on the surface of the base material 1. After that, it is wound on the winding roll 18 via the guide rolls 15, 16 and 17.

[Thickness of layer A]
The thickness of the A layer in the present invention can be determined by evaluation by XPS. Specifically, argon ion etching was performed from the outermost surface of the A layer in the _{direction of the base material by 5 nm in terms of SiO 2} equivalent thickness, and the portion where the metal element content ratio became 1.0 atm% or less for the first time was defined as the interface reference surface. When, the thickness of the outermost surface of the A layer from the interface reference plane is defined as the thickness of the A layer. When a plurality of metal elements are present, the interface reference plane is a portion where the total atomic concentration thereof is 1.0 atm% or less. When the base material contains a metal element similar to the metal element contained in the A layer, the interface reference plane is a portion where the atomic concentration ratio of the element not present in the A layer exceeds 10 atm%. do.

The thickness of the A layer is preferably 20 nm or more, preferably 500 nm or less. When the thickness is 20 nm or more, it is possible to prevent a region that is not formed as a layer from being generated and the gas barrier property cannot be ensured. Further, when the thickness of the layer A is 500 nm or less, it is possible to prevent cracks from easily forming, and it is possible to improve bending resistance and stretchability. From the above viewpoint, the thickness of the A layer is more preferably 30 nm or more and 300 nm or less.

[Base material]
The base material used in the present invention preferably has a film form from the viewpoint of ensuring 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. As the type of film, non-stretched, uniaxially stretched, biaxially stretched film or the like may be used.

The material of the base material used in the present invention is not particularly limited, but it is preferable that the material is mainly composed of an organic polymer. Examples of the organic polymer 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 and polycarbonates. Examples thereof include various polymers such as polystyrene, polyvinyl alcohol, saponified product of ethylene vinyl acetate copolymer, polyacrylonitrile, and polyacetal. Among these, it is preferable to use cyclic polyolefin or polyethylene terephthalate having excellent transparency, versatility, and mechanical properties. Further, the organic polymer may be either a homopolymer or a copolymer, only one type may be used as the organic polymer, or a plurality of types may be blended and used.

The surface of the base material on the side forming the A layer is composed of corona treatment, plasma treatment, ultraviolet treatment, ion bombard treatment, solvent treatment, organic or inorganic substances, or a mixture thereof in order to improve adhesion and smoothness. Pretreatment such as formation treatment of an anchor coat layer may be performed. Further, on the opposite side of the side forming the A layer, a coating layer of an organic substance, an inorganic substance, or a mixture thereof is laminated for the purpose of improving the slipperiness when winding the base material and the scratch resistance of the base material. You may.

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

[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 base material and the other surface is in contact with the A layer. Further, it is more preferable that the anchor coat layer contains a structure obtained by cross-linking a polyurethane compound having an aromatic ring structure. If there are defects such as protrusions and scratches on the base material, pinholes and cracks may also occur in the A layer laminated on the base material starting from the above defects, and the gas barrier property and bending resistance may be impaired. Therefore, it is preferable to provide an anchor coat layer. Further, even when the difference in thermal dimensional stability between the base material and the layer A is large, the gas barrier property and the flexibility may decrease. Therefore, it is preferable to provide the anchor coat layer. Further, the anchor coat layer used in the present invention preferably contains a structure obtained by cross-linking a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and bending resistance, and further, it is not ethylenically. More preferably, it contains a saturated compound, a photopolymerization initiator, an organosilicon compound and / or an inorganic silicon compound.

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

Examples of the epoxy (meth) acrylate having a hydroxyl group and an aromatic ring in the molecule include bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, hydroquinone and other aromatic glycol diepoxy compounds. It can be obtained by reacting with a (meth) acrylic acid derivative.

Examples of the diol compound include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 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-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4 4-Tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4'-(2-norbornenilidene) diphenol, 4,4' -Dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropyridenephenol, 4,4'-isopropyridenebin diol, cyclopentane-1,2-diol, cyclohexane-1,2- Glycol, 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 the diisocyanate compound include 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4-diphenylmethane diisocyanate. Aromatic diisocyanates such as, ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, aliphatic diisocyanate compounds such as lysine triisocyanate, etc. Examples thereof include 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.

The component ratios of the epoxy (meth) acrylate, the diol compound, and the diisocyanate compound having a hydroxyl group and an aromatic ring in the molecule are not particularly limited as long as they have a desired weight average molecular weight. The weight average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. When the weight average molecular weight (Mw) is 5,000 to 100,000, it is preferable because the obtained cured film has excellent thermal dimensional stability and bending resistance. The weight average molecular weight (Mw) in the present invention is a value measured by a gel permeation chromatography method and converted into standard polystyrene.

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

The content of the ethylenically unsaturated compound is not particularly limited, but is in the range of 5 to 90% by mass based on 100% by mass of the total amount of the polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and surface protection performance. It is preferably in the range of 10 to 80% by mass, and more preferably in the range of 10 to 80% by mass.

The material of the photopolymerization initiator is not particularly limited as long as it can maintain the gas barrier property and bending resistance of the laminate of the present invention. Examples of the photopolymerization initiator that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenylketone, and 2-hydroxy-2-methyl. -1-Phenyl-Propane-1-one, 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-Hirodoxy-1- {4 -[4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglycolic acid methyl ester, 2-methyl-1- (4-methylthiophenyl) ) -2-Molholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone and other alkylphenone-based photopolymerization initiators, 2,4,6-trimethylbenzoyl-diphenyl-phosphenyl oxide, bis (2,4,6- Acylphosphine oxide-based photopolymerization initiator such as trimethylbenzoyl) -phenylphosphinoxide, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1) -Il) -Phenyl) Photopolymerization with a titanosen-based photopolymerization initiator such as titanium, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and other oxime ester structures An initiator and the like can be mentioned.

Among these, from the viewpoint of curability and surface protection performance, 1-hydroxy-cyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6- A photopolymerization initiator selected from trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable. In addition, these may be used in a single composition, or two or more components may be mixed and used.

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

Examples of the organic silicon compound include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltri. Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Examples thereof include trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isopropylpropyltriethoxysilane.

Among these, selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane from the viewpoint of curability and polymerization activity by irradiation with active energy rays. At least one organosilicon compound is preferred. In addition, these may be used in a single composition, or two or more components may be mixed and used.

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

As the inorganic silicon compound, silica particles are preferable from the viewpoint 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. .. The primary particle diameter referred to here refers to the particle diameter d obtained by applying the specific surface area s obtained by the 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 further preferably 500 nm or more and 1,000 nm or less. If the thickness of the anchor coat layer is thinner than 200 nm, it may not be possible to suppress the adverse effects of defects such as protrusions and scratches existing on the base material. When the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer is lowered, the uneven shape of the surface of the A layer laminated on the anchor coat layer is also increased, and the vapor deposition film to be laminated becomes dense. It is difficult, and it may be difficult to obtain the effect of improving the gas barrier property. Here, the thickness of the anchor coat layer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

The arithmetic average roughness Ra of the anchor coat layer is preferably 10 nm or less. When Ra is set to 10 nm or less, a homogeneous layer A is easily formed on the anchor coat layer, and the reproducibility of gas barrier properties is improved, which is preferable. When Ra on the surface of the anchor coat layer is larger than 10 nm, the uneven shape of the surface of the A layer on the anchor coat layer also becomes large, the vapor-deposited film is difficult to become dense, and the effect of improving the gas barrier property may be difficult to obtain. In addition, cracks are likely to occur due to stress concentration in a portion having many irregularities, which may cause a decrease in 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. Ra of the anchor coat layer in the present invention can be measured using an atomic force microscope (AFM) or the like.

When the anchor coat layer is applied to the laminate of the present invention, as a means for applying the coating liquid containing the resin forming the anchor coat layer, first, a paint containing a polyurethane compound having an aromatic ring structure is dried on the base material. It is preferable to adjust the solid content concentration so that the thickness of the coating material becomes a desired thickness, and apply 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. .. Further, in the present invention, it is preferable to dilute the coating material containing the polyurethane compound having an aromatic ring structure with an organic solvent from the viewpoint of coating suitability.

Specifically, the solid content concentration is diluted to 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, ethylbutyl ether, or tetrahydrofuran. It is preferable to use it. These solvents may be used alone or in combination of two or more. In addition, various additives can be added to the paint forming the anchor coat layer, if necessary. For example, catalysts, antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers, surfactants, leveling agents, antistatic agents and the like can be used.

Then, it is preferable to dry the coating film after coating to remove the diluting solvent. Here, the heat source used for drying is not particularly limited, and any heat source such as a steam heater, an electric heater, or an infrared heater can be used. In order to improve the gas barrier property, the heating temperature is preferably 50 to 150 ° C. The heat treatment time is preferably several seconds to one hour. Further, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Further, during the drying treatment, the heat treatment may be performed while adjusting the humidity in the range of 20 to 90% RH in relative humidity. The heat treatment may be carried out in the air or while enclosing an inert gas.

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

The active energy ray to be applied in such a case is not particularly limited as long as the anchor coat layer can be cured, but it is preferable to use ultraviolet treatment from the viewpoint of versatility and efficiency. As the ultraviolet source, known sources such as a high-pressure mercury lamp, a metal halide lamp, a microwave-type electrodeless lamp, a low-pressure mercury lamp, and a xenon lamp can be used. Further, the active energy ray is preferably used in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of curing efficiency. The ultraviolet treatment may be performed under atmospheric pressure or reduced pressure, but from the viewpoint of versatility and production efficiency, it is preferable to perform ultraviolet treatment under atmospheric pressure in the present invention. The oxygen concentration at the time of performing the ultraviolet treatment is preferably 1.0% or less, more preferably 0.5% or less, from the viewpoint of controlling the degree of cross-linking of the anchor coat layer. Relative humidity may be arbitrary.

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

Preferably the integrated light quantity of ultraviolet irradiation is ^{0.1~1.0J / cm 2, 0.2~0.6J / cm} 2 is more preferable. When the integrated light intensity is 0.1 J / cm ² or more, a desired degree of cross-linking of the anchor coat layer can be obtained, which is preferable. Further, when the integrated light intensity is 1.0 J / cm ² or less, damage to the base material can be reduced, which is preferable.

[Other layers]
An overcoat layer is formed on the outermost surface of the laminate of the present invention, that is, on the layer A, for the purpose of improving printability and adhesion to an adhesive layer, etc., as long as the gas barrier property is not deteriorated. Alternatively, it may have a laminated structure in which an adhesive layer or a film made of an organic polymer compound for bonding to an element or the like is laminated. Further, a low refractive index layer may be formed to improve the optical characteristics. The outermost surface here means the surface of the A layer after the A layer is laminated on the base material.

[Use of laminate]
Since the laminate of the present invention has a high gas barrier property, it can be suitably used as a gas barrier film. Further, the laminate of the present invention can be used for various organic elements. For example, it can be suitably used for organic elements such as solar cells, flexible circuit base materials, organic EL lighting, and flexible organic EL displays. Further, taking advantage of its high barrier property, it can be suitably used as an exterior material for lithium ion batteries and a packaging material for pharmaceuticals.

[Organic element]
A preferred embodiment of the organic device of the present invention is an organic device sealed with the above-mentioned laminate. According to this aspect, it is possible to obtain an element having high durability and excellent appearance quality.

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.

[Evaluation method]
(1) Composition and thickness of layer A The composition analysis of layer A of the laminated body was performed by X-ray photoelectron spectroscopy (XPS). From the outermost surface of layer A to a depth of 10 nm, etching and composition analysis are repeated by 5 nm each with a thickness converted _{to SiO 2} by argon ion etching, and thereafter, converted _{to SiO 2 until the atomic concentration of the metal element M becomes 1.0 atm% or less.} Etching and composition analysis were repeated for each thickness of 5 nm.
The peaks used in the analysis were 2 s for magnesium, 2 p for silicon, and 1 s for oxygen.

The XPS measurement conditions were as follows.
-Device: PHI5000 VersaProbeII (manufactured by ULVAC-PHI)
-Excited X-ray: monochromatic AlKα
・ Analysis range: φ100 μm
・ Photoelectron escape angle: 45 °
-Ar ion etching: 2.0 kV, raster size 2 x 2.

(2) water vapor transmission rate ^{(g / (m 2 · 24hr} · atm))
The water vapor transmission rate of the laminate is 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 cm ^2. )) Was measured. The number of samples was 2 samples per level. Averaged data obtained was measured in the two samples, and two significant figures, an average value in the levels were the values water vapor permeability and ^{(g / (m 2 · 24hr} · atm)).

(3) Chemical resistance test 5 mL of an etching solution (iron chloride II: 27% by mass, hydrochloric acid: 10% by mass) was dropped on the surface of the A layer of a 100 × 100 mm laminate in an environment of 25 ° C., and 10 minutes later. After wiping off the etching solution, the water vapor transmission rate was measured and evaluated according to the following criteria. Incidentally, the water vapor permeability before chemical resistance tests, for those of non-measurable ^{(0.5g / (m 2 · 24hr} · atm)) above), was evaluated as "non-evaluation".

◯: Less than 10 times the water vapor transmission rate before the chemical resistance test.

X: 10 times or more the water vapor transmission rate before the chemical resistance test. Or water vapor transmission rate after the chemical resistance test unmeasurable ^{(0.5g / (m 2 · 24hr} · atm)) above).

(4) Positron lifetime and pore radius distribution The positron lifetime and pore radius distribution were measured by the positron beam method (the positron annihilation lifetime measurement method for thin films). The sample to be measured was attached to a 15 mm × 15 mm square Si wafer and evacuated at room temperature, and then the measurement was performed. The measurement conditions are as follows.
・ Equipment: Small positron beam generator PALS200A manufactured by Fuji Invac
- positron source: ²² Na based positron beam-gamma ray detector: BaF ₂ manufactured scintillator + photomultiplier and equipment constants: 255~278ps, 24.55ps / ch
・ Beam intensity: 1 keV
・ Measurement depth: around 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 with three or four components by the nonlinear least squares program POSITRONFIT.

(Example 1)
As a base material, a polyethylene terephthalate film having a thickness of 50 μm (“Lumilar” (registered trademark) U48 manufactured by Toray Industries, Inc.) was used.
(Formation of layer A)
Using the take-up type vapor deposition apparatus shown in FIG. 3, MgO + SiO ₂ layers as A layer were provided on the surface of the base material by an electron beam (EB) vapor deposition method aiming at a thickness of 200 nm.

The specific operation is as follows. First, as a vapor 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 are heated in advance at 100 ° C. for 8 hours, respectively. went. Subsequently, each material (deposited material B: MgO, vapor deposition material C: SiO ₂ ) was set in the carbon hearth liner 11 as shown in FIG. The material area ratio of MgO and SiO ₂ was set to MgO: SiO ₂ = 2: 1. In the take-up chamber 5, the unwinding roll 6 is set so that the surface of the base material 1 on which the A layer is provided faces the hearth liner 11, and the unwinding roll is unwound via the guide rolls 7, 8 and 9. I passed it through the main drum 10. At this time, the temperature of the main drum was controlled to −15 ° C. Next, the pressure inside the vapor deposition apparatus 4 was reduced by a vacuum pump ^{to obtain 5.0 × 10 -3} Pa or less. _{Next, MgO and SiO 2} were uniformly heated using one electron gun (hereinafter, EB gun) 13 as a heating source. The EB condition was such that the acceleration voltage was 10 kV, and the A layer was formed on the surface of the base material. The thickness of the A layer to be formed was adjusted by the applied current and the film transport speed. Then, it was wound on the winding roll 18 via the guide rolls 15, 16 and 17.

Subsequently, test pieces were cut out from the obtained 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 base material on which an anchor coat layer was formed was used as the base material according to the following procedure. The results are shown in Tables 1 and 2.

(Synthesis of polyurethane compound having aromatic ring structure)
Put 300 parts by mass of bisphenol A diglycidyl ether acrylic adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 3000A) and 710 parts by mass of ethyl acetate in a 5-liter four-necked flask, and the internal temperature becomes 60 ° C. I warmed it up. 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.) was added dropwise over 1 hour with stirring. The reaction was continued for 2 hours after the completion of the dropping, and then 25 parts by mass of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. The reaction was continued for 5 hours after the dropping to obtain a polyurethane compound having an aromatic ring structure having a weight average molecular weight of 20,000.

(Formation of anchor coat layer)
As a base material, a polyethylene terephthalate film having a thickness of 50 μm (“Lumilar” (registered trademark) U48 manufactured by Toray Industries, Inc.) was used.

As a coating liquid for forming the anchor coat layer, 150 parts by mass of the polyurethane compound and 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: "Light acrylate" (registered trademark) DPE-6A), 1 -Hydroxy-cyclohexylphenyl ketone (BASF Japan, trade name: "IRGACURE" (registered trademark) 184) in 5 parts by mass, 3-methacryloxypropylmethyldiethoxysilane (Shinetsu Silicone, trade name: KBM-503) ) By 3 parts by mass, ethyl acetate by 170 parts by mass, toluene by 350 parts by mass, and cyclohexanone by 170 parts by mass to prepare a coating solution. Next, the coating liquid was applied onto the substrate with a microgravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, dried, and then subjected to ultraviolet treatment under the following conditions to a thickness of 1 μm. An anchor coat layer was provided.

Ultraviolet processing equipment: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: N ₂ (Nitrogen Inert BOX)
Ultraviolet source: Microwave type electrodeless lamp Integrated light intensity: 400mJ / cm ²
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 and SiO _{2 was set to MgO: SiO 2 = 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 MgO and SiO ₂ were irradiated with EB at a time division ratio of 2: 1. The results are shown in Tables 1 and 2.

(Example 6)
The laminated body was obtained in the same manner as in Example 2 except that the vapor deposition materials B and C were arranged as shown in FIG. 5 and _{the material area ratio of MgO and SiO 2} was set to MgO: SiO _{2 = 1: 2.} rice field. The results are shown in Tables 1 and 2.

(Comparative Example 1)
The laminated body was obtained in the same manner as in Example 2 except that the vapor deposition materials B and C were arranged as shown in FIG. 5 and _{the material area ratio of MgO and SiO 2} was set to MgO: SiO _{2 = 2: 1.} rice field. 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 and SiO _{2 was set to MgO: SiO 2 = 5: 1.} The results are shown in Tables 1 and 2.

(Comparative Example 3)
Granular magnesium oxide MgO (purity 99.9%) having a size of about 2 to 5 mm was used as the vapor deposition material, and laminated in the same manner as in Example 2 except that it was set on a carbon hearth liner 11 having no partition. I got a body. 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 vapor 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, in Examples 1, 2, 4 and 6 in which the average composition M / (M + Si) value of the surface 10 nm is small (the ratio of Si is large), the deterioration of the water vapor barrier property due to the chemical resistance is small. This is because the layer has excellent chemical resistance due to the high concentration _{of SiO 2} near the surface.

On the other hand, in Comparative Examples 1, 2 and 4, since the Mg ratio is high for the entire A layer, the A layer disappears in the chemical resistance test and the water vapor barrier property deteriorates. Further, in Comparative Example 4, since the Si ratio of the entire A layer is high and the chemical resistance is excellent, the A layer does not disappear in the chemical resistance test but lacks the denseness. Therefore, the water vapor barrier before and after the chemical resistance test. Sex is not expressed.

Since the laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, etc., it can be usefully used, for example, as a packaging material for foods, pharmaceuticals, etc., and as a member for electronic devices such as flat-screen TVs, solar cells, etc. , Applications are not limited to these.

1 Base material 2 A layer 3 Anchor coat layer 4 Rewind-type electron beam (EB) vapor deposition equipment 5 Wind-up chamber 6 Unwind rolls 7, 8, 9 Unwind side guide rolls 10 Main drum 11 Haas liner 12 Evaporation material 13 Electrons Gun 14 Electron wire 15, 16, 17 Winding side guide roll 18 Winding roll 19 Deposited material B
20 Thin-film deposition material C

Claims (11)

An A layer containing silicon Si, a metal element M, and oxygen O is provided on at least one surface of the base material, and the average atomic concentration (atm%) ratio M measured by X-ray photoelectron spectroscopy having a thickness of 10 nm from the outermost surface of the A layer. A laminate in which / (M + Si) is 0 to 0.40. The laminate according to claim 1, wherein the layer A includes a portion in which the atomic concentration (atm%) ratio M / (M + Si) in the thickness direction is continuously inclined. The laminate according to claim 1 or 2, wherein the layer A is a single layer. The atomic concentration of the layer A (atm%) Ratio M / (M + Si), the atomic concentration ratio _{M B} near atomic concentration ratio _{M A} and the substrate in the vicinity of the outermost surface is the relation of _M A _{<M B,} wherein Item 3. The laminate according to any one of Items 1 to 3. The laminate according to any one of claims 1 to 4, wherein the layer A has an average lifetime of 0.935 ns or less as measured by the positron beam method. The laminate according to any one of claims 1 to 5, wherein the metal element of the layer A is at least one selected from the group consisting of magnesium, calcium, and zinc. The laminate according to any one of claims 1 to 6, wherein the layer A contains magnesium oxide and silicon oxide. Regarding the average composition of the A layer in the thickness direction, the magnesium (Mg) atomic concentration is 8 to 30 (atm%), the silicon (Si) atomic concentration is 6 to 25 (atm%), and the oxygen (O) atomic concentration is 50 to 50. The laminate according to any one of claims 1 to 7, which is 70 (atm%). The claim that the ratio Mg / (Mg + Si) of the atomic concentration (atm%) of magnesium (Mg) atom and silicon (Si) atom is 0.30 to 0.80 with respect to the average composition in the thickness direction of the layer A. The laminate according to any one of 1 to 8. The method for producing a laminate according to any one of claims 1 to 9, wherein the method for forming the layer A is a vacuum vapor deposition method. An organic device sealed with the laminate according to any one of claims 1 to 9.

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