Laminate, method for manufacturing a laminate, and organic element

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, a metal element and oxygen and B layer containing silicon in the stated order.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a laminate used in materials that require high gas barrier properties. [Background technology]

[0002] Gas barrier films, formed by creating a vapor-deposited layer of inorganic materials (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 chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition, are used as packaging materials for food and pharmaceuticals that require the blocking of various gases such as water vapor and oxygen, and as components for electronic devices such as electronic paper and solar cells. In these components, the water vapor transmission rate is 5.0 × 10⁻⁶. -3 g / (m 2 High gas barrier properties (below 24hr·atm) are required.

[0003] As one method to satisfy high gas barrier properties, a gas barrier film has been proposed in which defects are prevented by a hole-filling effect by alternately laminating organic and inorganic layers (Patent Document 1), and a gas barrier film in which a ZnO-SiO2 system film is formed on a film substrate by sputtering using a target mainly composed of ZnO and SiO2 (Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2005-324406 [Patent Document 2] Japanese Patent Publication No. 2013-147710 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, by alternately laminating organic and inorganic layers as in Patent Document 1, it is possible to exhibit high barrier properties. However, there is a problem in that the number of processes increases due to the lamination, resulting in high costs. In addition, a laminate having a gas barrier layer mainly composed of ZnO and SiO2 as in Patent Document 2 can exhibit high barrier properties with a single layer. However, ZnO has poor chemical resistance, and the gas barrier layer has poor chemical resistance. When the film thickness of the gas barrier layer is reduced, the abrasion resistance becomes poor, and there are problems such as the film being easily scratched during film conveyance or post-processing.

[0006] In view of the background of such prior art, an object of the present invention is to provide a laminate having a simple structure, high gas barrier properties, and excellent chemical resistance and abrasion resistance.

Means for Solving the Problems

[0007] In order to solve such problems, the present invention employs the following means. That is, it is as follows. (1) A laminate having an A layer containing silicon, a metal element, and oxygen and a B layer containing silicon in this order on at least one side of a substrate.

Effects of the Invention

[0008] According to the present invention, it is possible to provide a laminate having high gas barrier properties and chemical resistance against water vapor.

Brief Description of the Drawings

[0009] [Figure 1] It is a cross-sectional view showing an example of the laminate of the present invention. [Figure 2] It is a cross-sectional view showing an example of the laminate of the present invention. [Figure 3] It is a schematic diagram schematically showing a winding electron beam evaporation apparatus for manufacturing the laminate of the present invention. [Figure 4] It is a view schematically showing the material arrangement for manufacturing the laminate of the present invention from above. [Figure 5]It is a schematic diagram schematically showing a roll-to-roll sputtering apparatus for manufacturing the laminate of the present invention. [Figure 6] It is a schematic diagram schematically showing a roll-to-roll electron beam evaporation apparatus for manufacturing the laminate of the present invention.

Mode for Carrying Out the Invention

[0010] [Laminate] A preferred embodiment of the laminate of the present invention is a laminate having an A layer containing silicon, a metal element, and oxygen and a B layer containing silicon in this order on at least one side of a substrate.

[0011] By adopting this embodiment, a laminate having a high gas barrier property and further excellent chemical resistance and abrasion resistance can be obtained. In the present invention, the metal element is a metal element other than silicon.

[0012] Examples of the metal element contained in the A layer include magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, tin, etc. From the viewpoint of gas barrier property, it is preferable that the metal element of the A layer is at least one selected from the group consisting of magnesium, calcium, and zinc, and from the viewpoints of deposition property and optical properties, magnesium is more preferable.

[0013] The forms of silicon and metal elements contained in the A layer are not limited to oxides, nitrides, oxynitrides, carbides, etc., but from the viewpoints of forming an amorphous film and gas barrier property, it is preferably contained as at least one compound selected from the group consisting of oxides, nitrides, oxynitrides, and carbides, and more preferably contained as at least one compound selected from the group consisting of oxides, nitrides, and oxynitrides. Among them, it is more preferable to contain magnesium oxide and silicon oxide. As long as the A layer contains silicon, a metal element, and oxygen, other inorganic compounds may be contained.

[0014] The A layer being oxygen-containing means that, as evaluated by X-ray photoelectron spectroscopy (XPS), the oxygen atom content is 10.0 atm% or more at the point where argon ion etching is performed from the outermost surface of the A layer to a position where the thickness of the A layer becomes half, based on the converted thickness of the SiO2 film. From the viewpoint of transparency and density, an oxygen atom content of 20.0 atm% or more is preferable, and 40.0 atm% or more is more preferable. The outermost surface of the A layer refers to the surface opposite to the surface of the A layer that is closest to the substrate.

[0015] From the viewpoint of gas barrier properties, the silicon contained in layer B is preferably in the form of oxides, nitrides, oxidized nitrides, carbides, etc., and from the viewpoint of optical properties, it is more preferably contained as at least one compound selected from the group consisting of oxides, nitrides, and oxidized nitrides.

[0016] In the present invention, it is preferable to have layers A and B in this order from the substrate side. Layer A contains silicon, a metal element, and oxygen to form a dense composite oxide film, which can exhibit high gas barrier properties. It is preferable to form layer B on layer A because it can fill defects in layer A, complement the gas barrier properties, and further impart chemical resistance and scratch resistance. If layers A and B are swapped, the desired gas barrier properties, chemical resistance, and scratch resistance may not be obtained.

[0017] As long as layers A and B are present in this order from the substrate side, other layers may exist between the substrate and layer A, or on top of layer B. For example, an anchor coat layer may be provided between the substrate and layer A to smooth the substrate. Alternatively, a wet coat layer or dry coat layer may be provided on top of layer B to provide further chemical resistance or adhesion to adhesives. Furthermore, other layers may exist between layers A and B.

[0018] Here, a layer refers to a region that has a finite thickness and a boundary surface that allows it to be distinguished from adjacent regions in the thickness direction. These can be distinguished by cross-sectional observation using a transmission electron microscope (TEM). More specifically, it refers to regions that can be distinguished by the presence or absence of discontinuous boundaries when the cross-section of the laminate is observed with a TEM. Even if the composition changes, if there is no boundary surface between them as described above, it is treated as a single layer.

[0019] In the present invention, from the viewpoint of gas barrier properties and chemical resistance, it is preferable that layer A and layer B are composed of different elements or composition ratios. For example, if the elements of layer A are M1 and M2, and the elements of layer B are M1, M2, and M3, they are considered to be composed of different elements. If the elements of layer A are M1, M2, and M3, and similarly the elements of layer B are also M1, M2, and M3, they are considered to be composed of the same elements. However, even if the elements of layer A and layer B are the same, as described above, if they have an interface that can be distinguished from adjacent parts in the thickness direction in a cross-sectional TEM, they are distinguished as separate layers. For example, even if the elements are the same, this can occur if the film composition ratio is significantly different and the film density is significantly different, or if the crystal structure is significantly different.

[0020] As a specific embodiment of the above, for example, from the viewpoint of adhesion, it is preferable that the B layer contains at least one metal element other than silicon, selected from the group consisting of tin, zirconium, titanium, aluminum, niobium, tantalum, and indium. From the viewpoint of film formation and chemical resistance, tin, zirconium, and titanium are more preferable. Furthermore, although their forms are not limited to oxides, nitrides, oxidized nitrides, carbides, etc., from the viewpoint of gas barrier properties and optical properties, it is preferable that they exist as oxides, nitrides, or oxidized nitrides. Among these, it is even more preferable to include tin oxide and silicon oxide or zirconium oxide and silicon oxide.

[0021] The A layer of the present invention preferably has an average lifetime of 0.935 ns or less, as measured by the positron beam method (thin film compatible positron annihilation lifetime measurement method) (see Chapter I, Section 1 and Chapter V, Section 2 of "The Science of Positron Measurement" (Japan Isotope Association)). The positron beam method is one of the positron annihilation lifetime measurement methods, which measures the time (on the order of several hundred ps to several tens of ns) from when a positron is incident on a sample until it annihilates, and is a method that non-destructively evaluates information regarding the size, number concentration, and even the size distribution of vacancies of approximately 0.1 to 10 nm from its annihilation lifetime. A radioactive isotope is used as the positron beam source. 22 This method differs significantly from conventional positron annihilation methods in that it uses a positron beam instead of Na, enabling the measurement of thin films with thicknesses of several hundred nanometers deposited on silicon or quartz substrates. From the obtained measurements, the average pore radius and pore number concentration can be determined using the nonlinear least-squares program POSITRONFIT. Pores and basic frameworks on the sub-nm order can be obtained by analyzing the average lifetimes of the third and fourth components.

[0022] Here, the third component refers to the average lifetime obtained by selecting the analysis for three components as the measurement condition for the average lifetime using the positron beam method, and the fourth component refers to the average lifetime obtained by selecting the analysis for four components as the measurement condition for the average lifetime using the positron beam method. When performing analysis with POSITRONFIT, the number of components in POSITRONFIT is determined from the number of peaks obtained from the pore radius distribution curve calculated using the distribution analysis program CONTIN based on the inverse Laplace transform method. The validity of the analysis is determined by the fact that the average pore radius calculated from POSITRONFIT matches the peak position of the pore radius distribution curve of CONTIN. In this invention, the average lifetime refers to the average lifetime of the third component. In positron beam analysis, if layer B or other layers exist on layer A, these layers are removed so that layer A becomes the outermost surface before analysis. Methods for removing layers on layer A include wet etching, dry etching, and theme peeling.

[0023] A lifetime of 0.935 ns or less results in a dense A layer, enabling high gas barrier properties. From the viewpoint of gas barrier properties, the lifetime measured by the positron beam method is preferably 0.912 ns or less, and more preferably 0.863 ns or less. Furthermore, while there is no particular lower limit to the lifetime, it is preferably 0.542 ns or more. A lifetime of 0.542 ns or more allows for sufficient flexibility.

[0024] In order to achieve an average lifetime of 0.935 ns or less as measured by the positron beam method of layer A as defined in this invention, this can be achieved, for example, by densely forming a composite oxide film in an appropriate composition ratio on a substrate with an arithmetic mean roughness Ra of 3.0 nm or less. Dense formation, as used here, means a state in which each oxide is mixed at the atomic level to form a dense network.

[0025] In the present invention, it is preferable that the A layer has a full width at half maximum (FWHM) of the oxygen atom (O1s) peak measured by X-ray photoelectron spectroscopy of 3.25 eV or less. The FWHM is calculated by taking the maximum value of the peak as F. max In that case, the peak intensity is F max This refers to the peak width at 2 / 2. A narrower half-width of the O1s peak leads to the formation of a more uniform bonding network structure, resulting in a denser film. From the viewpoint of bonding uniformity and barrier properties, a value of 3.00 eV or less is more preferable, and 2.75 eV or less is even more preferable. The lower limit is not particularly limited, but it is preferably 1.65 eV or higher.

[0026] Regarding the composition of layer A of the present invention, the magnesium (Mg) atom concentration is 5 to 50 (atm%). A laminate with a silicon (Si) atom concentration of 2 to 30 (atm%) and an oxygen (O) atom concentration of 45 to 70 (atm%) is preferred. The "~" symbol indicates "greater than or equal to" and "less than or equal to."

[0027] The composition ratio of layer A can be measured by X-ray photoelectron spectroscopy (XPS). After removing layer B by argon ion etching, the layer is removed from the surface side by argon ion etching until the thickness of layer A is halved, and the content ratio of each element is measured.

[0028] From the viewpoint of suppressing the formation of a crystalline layer in layer A and its susceptibility to cracking, it is preferable that the magnesium atom concentration is 50 atm% or less and / or the silicon atom concentration is 2 atm% or more.

[0029] From the viewpoint of ensuring a sufficient proportion of silicate bonds in layer A, improving density, and exhibiting gas barrier properties, it is preferable that the magnesium atom concentration is 5 atm% or more and / or the silicon atom concentration is 30 atm% or less. A silicate bond is a bond between silicon (Si) and a metal (M) via oxygen (O), and can be written as Si-OM.

[0030] From the viewpoint of suppressing a decrease in light transmittance due to insufficient oxidation of magnesium and silicon, it is preferable that the oxygen atom concentration be 45 atm% or higher. Furthermore, from the viewpoint of suppressing an increase in voids and defects due to excessive oxygen incorporation and exhibiting gas barrier properties, it is preferable that the oxygen atom concentration be 70 atm% or lower.

[0031] From the above viewpoint, regarding the composition of layer A of the present invention, it is more preferable that 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%), and even more preferable that 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%).

[0032] Furthermore, in terms of the ratio of atomic concentrations (atm%), (Mg+Si):O = 1:1.25 to 2 is preferable. From the viewpoint of gas barrier properties and optical properties, (Mg+Si):O = 1:1.40 to 1.75 is more preferable.

[0033] Regarding the composition of layer A of the present invention, it is preferable that the atomic concentration (atm%) ratio Mg / (Mg+Si) of magnesium (Mg) atoms to silicon (Si) atoms is 0.45 to 0.80. By having an atomic concentration (atm%) ratio of Mg / (Mg+Si) ≥ 0.45, the proportion of silicate bonds in layer A is made sufficient, improving density and enabling gas barrier properties. By having an atomic concentration (atm%) ratio Mg / (Mg+Si) ≤ 0.80, the presence of crystalline parts in layer A is suppressed, and the likelihood of cracking is reduced. From a similar viewpoint, an atomic concentration (atm%) ratio Mg / (Mg+Si) of 0.50 to 0.78 is more preferable, and 0.55 to 0.76 is even more preferable.

[0034] The thickness of layer A in this invention can be obtained by evaluation using a transmission electron microscope (TEM). The thickness of layer A is preferably 5 nm or more, and preferably 500 nm or less. A thickness of 5 nm or more can suppress the occurrence of regions that are not formed as a layer, which would compromise the gas barrier properties. Furthermore, a thickness of 500 nm or less can suppress the tendency for cracks to form, and improve flexibility and stretchability. From the above viewpoint, a thickness of 10 nm or more and 300 nm or less is more preferable.

[0035] Regarding the composition of layer B of the present invention, it is preferable that the laminate has a tin (Sn) atom concentration of 10-30 (atm%), a silicon (Si) atom concentration of 10-30 (atm%), and an oxygen (O) atom concentration of 50-75 (atm%). The composition ratio of layer B can be measured by XPS method, similar to layer A. The layer is removed from the surface by argon ion etching until the thickness of layer B is 1 / 2, and the content ratio of each element is measured.

[0036] From the viewpoint of ensuring sufficient chemical resistance, it is preferable that the tin atom concentration is 10 atm% or more and / or the silicon atom concentration is 30 atm% or less.

[0037] From the perspective of exhibiting gas barrier properties and ensuring sufficient optical properties, it is preferable that the tin atom concentration is 30 atm% or less and / or the silicon atom concentration is 10 atm% or more.

[0038] The thickness of the B layer in the present invention can be obtained by evaluation using a transmission electron microscope (TEM). The thickness of the B layer is preferably 10 nm or more and 200 nm or less. When the thickness of the B layer is 10 nm or more, the generation of regions that are not formed as a layer can be suppressed, and sufficient gas barrier properties, scratch resistance, and chemical resistance can be achieved. Also, when the thickness of the B layer is 200 nm or less, the tendency for cracks to occur can be suppressed, and sufficient flexural resistance and optical properties can be achieved. From the same perspective, the thickness of the B layer is more preferably 20 nm or more and 100 nm or less.

[0039] The laminate of the present invention has a water vapor transmission rate of 5.0×10 -2 g / m 2 / day or less, which is preferable. From the perspective of use in high-grade packaging materials and electronic device applications that require relatively high gas barrier properties, the water vapor transmission rate of the laminate of the present invention is more preferably 1.0×10 -2 g / m 2 / day or less. Also, the lower limit of the water vapor transmission rate is not particularly limited, but if the film becomes too dense more than necessary, cracks are likely to occur. Therefore, the water vapor transmission rate of the laminate of the present invention is preferably 1.0×10 -4 g / m 2 / day or more.

[0040] [Method for manufacturing the A layer] There are no particular limitations on the method for forming layer A, and methods such as vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, atomic layer deposition, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD, laser CVD, thermal CVD, and coating can be used. From the viewpoint of manufacturing cost, environmental impact, and gas barrier properties, vacuum deposition is preferred. From the viewpoint of compound deposition, electron beam (EB) deposition and ion beam-assisted deposition (IBAD) are even more preferred among vacuum deposition methods.

[0041] An example of a method for forming layer A using a winding-type deposition 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 (EB) deposition. First, granular materials B and C, approximately 2 to 5 mm in size, are arranged as deposition materials in an area ratio of 1:1 as shown in Figure 4. The deposition materials are not limited to granules; molded bodies such as square or tablet shapes may also be used. Furthermore, the arrangement of the deposition source materials may be adjusted so that layer A has the desired film structure, by adjusting the arrangement ratio of materials B and C, or by using materials that are pre-mixed or sintered. In addition, if the deposition materials are hygroscopic, moisture in the materials may be incorporated into layer A, potentially preventing the acquisition of the desired film composition and physical properties. Therefore, it is preferable to dehydrate the materials by heating before use. In the winding chamber 5, the side of substrate 1 on which layer A is to be applied is set on the unwinding roll 6 so that it faces the hearth liner 11, and the material is unwound and passed through the main drum 10 via guide rolls 7, 8, and 9. Next, the vacuum pump reduces the pressure inside the deposition apparatus 4, and 5.0 × 10 -3 A vacuum of less than Pa is obtained. The ultimate vacuum is 5.0 × 10⁻⁶. -3 A vacuum of 5.0 × 10⁻⁶ Pa or less is preferable. -3If the pressure is greater than Pa, residual gas may be incorporated into the A layer, potentially preventing the acquisition of the desired film composition and physical properties. The temperature of the main drum 10 is set to -10°C as an example. From the viewpoint of preventing thermal damage to the substrate, a temperature of 20°C or lower is preferable, and more preferably 0°C or lower. Next, an electron gun (hereinafter referred to as EB gun) 13 is used as a heating source, and the EB gun is set to an acceleration voltage of 10kV. The acceleration current and film transport speed are adjusted so that the thickness of the A layer to be formed is approximately 200nm, and the A layer is formed on the surface of the substrate 1. After that, it is wound onto the winding roll 18 via guide rolls 15, 16, and 17.

[0042] [Method for manufacturing layer B] There are no particular limitations on the method for forming the B layer, and methods such as vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, atomic layer deposition, plasma polymerization, atmospheric pressure plasma polymerization, plasma CVD, laser CVD, thermal CVD, and coating can be used. From the viewpoint of efficiently obtaining the desired chemical resistance and scratch resistance in a thin film, the sputtering method is preferable, and from the viewpoint of cost, the vacuum deposition method is preferable.

[0043] An example of a method for forming layer B using a winding sputtering apparatus (Figure 5) is shown. A compound thin film of materials D and E is formed as layer B on top of layer A of a substrate 34, which has layer A formed on its surface by sputtering. A sputtering target, which is a mixed sintered material formed of materials D and E, is placed on the sputtering electrode 28, and sputtering is performed using argon gas and oxygen gas to form layer B on layer A of the substrate 34 with a thickness of approximately 50 nm. Specifically, first, in the winding chamber 22 of the sputtering apparatus 21, where the sputtering target, which is a mixed sintered material formed of materials D and E, is placed on the sputtering electrode 28, the side of the substrate 34 on which layer B is to be formed (the side on which layer A is formed) is set on the unwinding roll 23 so that it faces the sputtering electrode 28, and then unwinds and passes through guide rolls 24, 25, and 26 to the main drum 27, which is controlled to a temperature of 100°C. Next, the pressure inside the sputtering apparatus 21 is reduced by a vacuum pump to 2.0 × 10⁻⁶ -3Obtain a vacuum of 5.0 × 10⁻⁶. -1 Argon and oxygen gases are introduced with an oxygen gas partial pressure of 40% to achieve a pressure of Pa, and a power input of 1,500 W is applied to the sputtering electrode 28 using a DC pulse power supply to generate an argon-oxygen gas plasma, thereby forming layer B on the surface of layer A of the substrate 34 by sputtering. The thickness of the formed layer B is adjusted by the film transport speed. Subsequently, the laminate is wound onto the winding roll 32 via guide rolls 29, 30, and 31 to obtain a laminate.

[0044] [Base material] The substrate used in the present invention is preferably in the form of a film from the viewpoint of ensuring flexibility. The film may be a single-layer film or a film of two or more layers, for example, a film produced by co-extrusion. The type of film may be an unoriented, uniaxially oriented, or biaxially oriented film.

[0045] The material of the base material used in the present invention is not particularly limited, but it is preferable that it mainly consists of an organic polymer. Examples of organic polymers that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymers, polyacrylonitrile, polyacetal, and various other polymers. Among these, amorphous cyclic polyolefins or polyethylene terephthalate, which have excellent transparency, versatility, and mechanical properties, are preferred. Furthermore, the organic polymer may be a homopolymer or a copolymer, and only one type of organic polymer may be used, or multiple types may be blended and used.

[0046] The surface of the substrate on which layer A is formed may be pre-treated to improve adhesion and smoothness, such as corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or formation of an anchor coat layer composed of organic or inorganic materials or mixtures thereof. Furthermore, on the opposite side of the substrate from which layer A is formed, a coating layer of organic or inorganic materials or mixtures thereof may be laminated to improve the slipperiness during winding and to increase the scratch resistance of the substrate.

[0047] The thickness of the substrate used in the present invention is not particularly limited, but from the viewpoint of ensuring flexibility, it is preferably 500 μm or less, and from the viewpoint of ensuring strength against tensile and impact, it is preferably 5 μm or more. Furthermore, from the viewpoint of ease of processing and handling the film, the thickness of the substrate is more preferably 10 μm or more and 150 μm or less.

[0048] [Anchor coat layer] The laminate of the present invention may have an anchor coat layer. Preferably, one side of the anchor coat layer is in contact with the substrate and the other side is in contact with the A layer. Furthermore, it is more preferable that the anchor coat layer includes 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 occur in the A layer laminated on the substrate starting from the defects, impairing gas barrier properties and flexibility, so it is preferable to provide an anchor coat layer. Also, if there is a large difference in thermal dimensional stability between the substrate and the A layer, gas barrier properties and flexibility may decrease, so it is preferable to provide an anchor coat layer. Furthermore, the anchor coat layer used in the present invention preferably includes a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and flexibility, and it is more preferable to include an ethylenically unsaturated compound, a photopolymerization initiator, an organosilicon compound and / or an inorganic silicon compound.

[0049] 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 its main chain or side chain, and can be obtained, for example, by polymerizing epoxy (meth)acrylate, diol compound, or diisocyanate compound having a hydroxyl group and an aromatic ring in its molecule.

[0050] Epoxy (meth)acrylates having a hydroxyl group and an aromatic ring in their molecule can be obtained by reacting diepoxy compounds of aromatic glycols such as bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, resorcinol, and hydroquinone with (meth)acrylic acid derivatives.

[0051] Examples of diol compounds include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 1,2-cyclohexane. Dimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-,m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4'-isopropylidenebinediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, etc. can be used. These can be used individually or in combination of two or more.

[0052] Examples of diisocyanate compounds include aromatic diisocyanates such as 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 2,4-diphenylmethanediisocyanate, and 4,4-diphenylmethanediisocyanate, as well as ethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylenediisocyanate. Examples 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 individually or in combination of two or more.

[0053] The component ratio of the epoxy (meth)acrylate, diol compound, and diisocyanate compound having a hydroxyl group and an aromatic ring in the molecule is not particularly limited as long as it is within the range of the desired weight-average molecular weight. In the present invention, the weight-average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure is preferably 5,000 to 100,000. A weight-average molecular weight (Mw) of 5,000 to 100,000 is preferable because it provides excellent thermal dimensional stability and flexural resistance of the resulting cured film. The weight-average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted to standard polystyrene.

[0054] Examples of ethylenically unsaturated compounds include di(meth)acrylates such as 1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate; polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and epoxy acrylates such as bisphenol A type epoxy di(meth)acrylate, bisphenol F type epoxy di(meth)acrylate, and bisphenol S type epoxy di(meth)acrylate. Among these, polyfunctional (meth)acrylates with excellent thermal dimensional stability and surface protection performance are preferred. These may be used in a single composition or as a mixture of two or more components.

[0055] The content of ethylenically unsaturated compounds is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, it is preferably in the range of 5 to 90% by mass, and more preferably in the range of 10 to 80% by mass, of the total amount of polyurethane compounds having an aromatic ring structure.

[0056] As a photopolymerization initiator, the material is not particularly limited as long as it can maintain the gas barrier properties and flexibility of the laminate of the present invention. Examples of photopolymerization initiators that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl 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-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl). Examples 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-diphenylphosphine 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-pyrrole-1-yl)-phenyl)titanium, and photopolymerization initiators having oxime ester structures such as 1,2-octanedione and 1-[4-(phenylthio)-,2-(O-benzoyloxime)].

[0057] Among these, photopolymerization initiators selected from 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred from the viewpoint of curability and surface protection performance. These may be used in a single composition or as a mixture of two or more components.

[0058] 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% by mass, and more preferably in the range of 0.1 to 5% by mass, of the total amount of polymerizable components.

[0059] Examples of organosilicon compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatetopropyltriethoxysilane.

[0060] Among these, at least one organosilicon compound selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is preferred from the viewpoint of curability and polymerization activity by active energy irradiation. Furthermore, these may be used in a single composition or as a mixture of two or more components.

[0061] The content of organosilicon compounds 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% by mass, and more preferably in the range of 0.1 to 5% by mass, of the total amount of polymerizable components.

[0062] As the inorganic silicon compound, silica particles are preferred from the viewpoint of surface protection performance and transparency, and more preferably the primary particle diameter of the silica particles is in the range of 1 to 300 nm, and more preferably in the range of 5 to 80 nm. The primary particle diameter referred to here is 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.

[0063] 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 less than 200 nm, it may not be possible to suppress the adverse effects of defects such as protrusions and scratches present on the substrate. If the thickness of the anchor coat layer is greater than 4,000 nm, the smoothness of the anchor coat layer decreases, the uneven shape of the surface of layer A laminated on the anchor coat layer also increases, making it difficult for the laminated vapor-deposited film to become dense, and it may be difficult to obtain the effect of improving gas barrier properties. The thickness of the anchor coat layer can be measured from cross-sectional observation images obtained by a transmission electron microscope (TEM).

[0064] The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. A Ra of 10 nm or less is preferable because it facilitates the formation of a homogeneous A layer on the anchor coat layer, improving the repeatability of the gas barrier properties. If the Ra of the surface of the anchor coat layer exceeds 10 nm, the surface irregularities of the A layer on the anchor coat layer also increase, making it difficult to achieve a dense vapor-deposited film and potentially reducing the gas barrier improvement effect. Furthermore, cracks due to stress concentration are more likely to occur in areas with many irregularities, which can lead to a decrease in the repeatability of the gas barrier properties. Therefore, in this invention, the Ra of the anchor coat layer is preferably 10 nm or less, and more preferably 5 nm or less. The Ra of the anchor coat layer in this invention can be measured using an atomic force microscope (AFM) or the like.

[0065] When applying an anchor coat layer to the laminate of the present invention, the coating liquid containing the resin that forms the anchor coat layer is preferably applied by first adjusting the solid content concentration of the coating containing a polyurethane compound having an aromatic ring structure on the substrate so that the thickness after drying is the desired thickness, and then applying it by, for example, the reverse coat method, gravure coat method, rod coat method, bar coat method, die coat method, spray coat method, spin coat method, etc. Furthermore, in the present invention, it is preferable to dilute the coating containing a polyurethane compound having an aromatic ring structure with an organic solvent from the viewpoint of coating suitability.

[0066] Specifically, it is preferable to dilute the paint to a solid content concentration of 10% by mass or less using hydrocarbon solvents such as xylene, toluene, methylcyclohexane, pentane, and hexane, or ether solvents such as dibutyl ether, ethyl butyl ether, and tetrahydrofuran. These solvents may be used individually or in mixtures of two or more. In addition, various additives can be added to the paint that forms the anchor coat layer as needed. For example, catalysts, antioxidants, light stabilizers, UV absorbers and other stabilizers, surfactants, leveling agents, and antistatic agents can be used.

[0067] Next, it is preferable to dry the applied coating film to remove the diluent. There are no particular restrictions on the heat source used for drying; any heat source such as a steam heater, electric heater, or infrared heater can be used. To improve gas barrier properties, it is preferable to heat the film at a temperature of 50 to 150°C. The heating treatment time is preferably from a few seconds to 1 hour. Furthermore, the temperature may be kept constant during the heating treatment, or it may be gradually changed. In addition, the humidity may be adjusted to a relative humidity of 20 to 90% RH during the drying treatment. The heating treatment may be carried out in the atmosphere or while sealing in an inert gas.

[0068] Next, it is preferable to apply an active energy ray irradiation treatment to the coating film containing a polyurethane compound having an aromatic ring structure after drying to crosslink the coating film and form an anchor coat layer.

[0069] In such cases, there are no particular restrictions on the active energy rays to be applied as long as they can harden the anchor coat layer, but from the viewpoint of versatility and efficiency, ultraviolet treatment is preferred. As ultraviolet light sources, known ones such as high-pressure mercury lamps, metal halide lamps, microwave-type electrodeless lamps, low-pressure mercury lamps, and xenon lamps can be used. Furthermore, from the viewpoint of hardening efficiency, the active energy rays are preferably used in an inert gas atmosphere such as nitrogen or argon. The ultraviolet treatment can be performed under either atmospheric pressure or reduced pressure, but from the viewpoint of versatility and production efficiency, the present invention prefers to perform the ultraviolet treatment under atmospheric pressure. The oxygen concentration when performing the ultraviolet treatment is preferably 1.0% or less, and more preferably 0.5% or less, from the viewpoint of controlling the degree of crosslinking of the anchor coat layer. The relative humidity can be arbitrary.

[0070] Known sources of ultraviolet light can be used, such as high-pressure mercury lamps, metal halide lamps, microwave-type electrodeless lamps, low-pressure mercury lamps, and xenon lamps.

[0071] The cumulative light intensity of UV irradiation is 0.1 to 1.0 J / cm². 2 Preferably, it is 0.2 to 0.6 J / cm². 2 A more preferable result is an integrated light quantity of 0.1 J / cm². 2 The above is preferable because it allows for the desired degree of crosslinking of the anchor coat layer. Also, the integrated light quantity is 1.0 J / cm². 2 The following are preferable because they minimize damage to the substrate.

[0072] [Other layers] On the outermost surface of the laminate of the present invention, an overcoat layer may be formed to improve printability and adhesion to adhesive layers, etc., within a range that does not reduce gas barrier properties. Alternatively, a laminated structure may be formed in which an adhesive layer or film made of an organic polymer compound for bonding to elements, etc., is laminated. Furthermore, a low refractive index layer may be formed to improve optical properties.

[0073] [Applications of laminates] Because the laminate of the present invention has high gas barrier properties, it can be suitably used as a gas barrier film. Furthermore, the laminate of the present invention can be used in various organic elements. For example, it can be suitably used in organic elements such as solar cells, flexible circuit boards, organic EL lighting, and flexible organic EL displays. In addition, taking advantage of its high barrier properties, it can be suitably used as an outer casing material for lithium-ion batteries and a packaging material for pharmaceuticals.

[0074] [Organic elements] A preferred embodiment of the organic element of the present invention is an organic element sealed in the above-mentioned laminate. This embodiment allows for an element with high durability and excellent appearance. [Examples]

[0075] The present invention will be described in detail below based on examples. However, the present invention is not limited to the following examples.

[0076] [Evaluation Method] (1) Thickness of each layer Samples for cross-sectional observation were prepared using a microsampling system (Hitachi, Ltd. FB-2000A) by the FIB method (specifically, based on the method described in "Polymer Surface Processing" (by Akira Iwamori), pp. 118-119). The cross-sections of the observation samples were observed at 200,000x magnification with an acceleration voltage of 300kV using a transmission electron microscope (Hitachi, Ltd. H-9000UHRII), and the thicknesses of layers A and B of the laminate were measured.

[0077] (2) Composition of Layer A and Layer B The compositional analysis of layers A and B of the laminate was performed by X-ray photoelectron spectroscopy (XPS). The content ratio of each element was measured at locations where the thickness of each layer was etched using argon ion etching to a point where the thickness of either layer A or B was halved, with the etching being equivalent to the thickness of SiO2. The peaks used in the analysis were 2s for magnesium, 2p for silicon, and 2p for zinc. 3 / 2 Suzu is 3D 5 / 2Oxygen was assumed to be 1 second.

[0078] The measurement conditions for XPS were as follows. • Equipment: PHI5000VersaProbeII (manufactured by ULVAC-FI) • Excitation X-rays: monochromatic AlKα • Analysis range: φ100μm • Photoelectron escape angle: 45° • Ar ion etching: 2.0kV, raster size 2x2 The full width at half maximum (FMAX) of the oxygen atom (O1s) peak was calculated using the Multipak analysis software included with the measurement device.

[0079] (3) Water vapor transmission rate (g / (m 2 (24-hour ATM) The water vapor transmission rate of the laminate was measured at a temperature of 40°C, a humidity of 90% RH, and a measurement area of ​​50 cm². 2 Under these conditions, measurements were taken using a water vapor transmission rate measuring device (model name: "DELTAPERM" (registered trademark)) manufactured by Technolox, a UK company. Two samples were taken per level. The data obtained from the two samples were averaged to two significant figures to determine the average value for that level, and this value was used to calculate the water vapor transmission rate (g / m³). 2 (24hr·atm))

[0080] (4) Chemical resistance test 5 mL of etching solution (iron(II) chloride: 27% by mass, hydrochloric acid: 10% by mass) was dropped onto the outermost surface (A or B layer surface) of a 100 × 100 mm laminate at 25°C. After 10 minutes, the etching solution was wiped off, and the water vapor transmission rate was measured and evaluated according to the following criteria.

[0081] ○: Less than 10 times the water vapor transmission rate before the chemical resistance test.

[0082] ×: Water vapor transmission rate is 10 times or more compared to the water vapor transmission rate before the chemical resistance test. Or, the water vapor transmission rate after the chemical resistance test is not measurable (0.5g / (m 2 ·24hr·atm)) or more). (5) Positron lifetime and pore radius distribution Positron lifetime and pore radius distribution were measured using the positron beam method (thin-film compatible positron annihilation lifetime measurement method). As a pretreatment for analysis, the B layer was removed according to the film thickness using 15% hydrofluoric acid. Then, the sample to be measured was attached to a 15 mm x 15 mm Si wafer, degassed under vacuum at room temperature, and measured. The measurement conditions are as follows. • Equipment: Fuji Invac PALS200A compact positron beam generator ·Positron source: 22 Na-based positron beam • Gamma-ray detector: BaF2 scintillator + photomultiplier tube ·Device constants: 255~278ps, 24.55ps / ch Beam intensity: 1 keV • Measurement depth: Approximately 0-100 nm (estimated) ·Measurement temperature: room temperature • Measurement atmosphere: Vacuum • Measurement count: Approximately 5,000,000 counts The measurement results were analyzed using the nonlinear least-squares program POSITRONFIT, performing either a 3-component or 4-component analysis.

[0083] (Example 1) (Synthesis of polyurethane compounds having an aromatic ring structure) In a 5-liter four-necked flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Epoxy Ester 3000A) and 710 parts by mass of ethyl acetate were added, and the mixture was heated to an internal temperature of 60°C. 0.2 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by mass of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise over 1 hour while stirring. The reaction was continued for 2 hours after the completion of the dropwise addition, and then 25 parts by mass of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise over 1 hour. The reaction was continued for 5 hours after the dropwise addition, yielding a polyurethane compound having an aromatic ring structure with a weight-average molecular weight of 20,000.

[0084] (Formation of anchor coat layer) A polyethylene terephthalate film with a thickness of 50 μm (Toray Industries, Inc.'s "Lumirror" (registered trademark) U48) was used as the base material.

[0085] As a coating solution for forming the anchor coat layer, a coating solution was prepared by combining 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: "Light Acrylate" (registered trademark) DPE-6A), 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan, trade name: "IRGACURE" (registered trademark) 184), 3 parts by mass of 3-methacryloxypropyl methyldiethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-503), 170 parts by mass of ethyl acetate, 350 parts by mass of toluene, and 170 parts by mass of cyclohexanone. Next, the coating solution was applied to the substrate using a microgravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100°C for 1 minute, and after drying, ultraviolet treatment was performed under the following conditions to form an anchor coat layer with a thickness of 1 μm on the substrate.

[0086] UV treatment device: LH10-10Q-G (manufactured by Fusion UV Systems Japan Co., Ltd.) Introduced gas: N2 (nitrogen inert box) UV light source: Microwave-type electrodeless lamp Total luminous intensity: 400 mJ / cm 2 Sample temperature control: Room temperature. (Formation of Layer A) Using the roll-type deposition apparatus shown in Figure 3, an MgO+SiO2 layer, designated as layer A, with a thickness of approximately 200 nm was deposited on the surface of the anchor coat layer of the substrate by electron beam (EB) deposition.

[0087] The specific procedure is as follows. First, granular magnesium oxide (MgO) (99.9% purity) and silicon dioxide (SiO2) (99.99% purity), each approximately 2-5 mm in size, were preheated at 100°C for 8 hours as deposition materials. Next, each material was set in a carbon hearth liner 11 as shown in Figure 4. The area ratio of the materials was set to MgO:SiO2 = 1:1. In the winding chamber 5, the side of the substrate 1 with layer A facing the hearth liner 11 was set on the unwinding roll 6 and unwound, passing through guide rolls 7, 8, and 9 to the main drum 10. At this time, the temperature of the main drum was controlled to -10°C. Next, the pressure inside the deposition apparatus 4 was reduced using a vacuum pump, and 5.0 × 10⁻⁶ -3 A pressure of less than Pa was obtained. Next, an electron gun (hereinafter referred to as EB gun) 13 was used as a heating source, and the heating ratio of MgO and SiO2 was controlled so that the ratio of atomic concentrations (atm%) was approximately Mg:Si = 2:1 for the film composition. The EB gun was set to an acceleration voltage of 10kV, and the acceleration current and film transport speed were adjusted so that the thickness of the A layer to be formed was approximately 200nm, and the A layer was formed on the surface of the substrate 1. After that, it was wound onto a winding roll 18 via guide rolls 15, 16, and 17.

[0088] (Formation of layer B) Following the formation of layer A, layer B was formed on layer A of the substrate 34 using a sputtering apparatus with the structure shown in Figure 5. A sputtering target made of silicon dioxide was placed on the sputtering electrode 28, and sputtering was performed using argon gas and oxygen gas to form an SiO2 layer as layer B on layer A of the substrate 34, with a thickness of approximately 50 nm.

[0089] The specific operation is as follows. First, in the winding chamber 22 of the sputtering apparatus 28, which has a silicon dioxide sputtering target installed on the sputtering electrode 28, the unwinding roll 23 is set so that the side of the substrate 34 on which layer B is to be formed (the side on which layer A is formed) faces the sputtering electrode 28, and the material is unwound and passed through the main drum 27, which is controlled to a temperature of 100°C, via the guide rolls 24, 25, and 26. Next, the pressure inside the sputtering apparatus 21 is reduced by a vacuum pump, and 2.0 × 10⁻⁶-3 We obtained a vacuum of less than Pa. Next, we measured the vacuum level at 5.0 × 10⁻⁶ -1 Argon and oxygen gases were introduced with an oxygen gas partial pressure of 10% to achieve a pressure of Pa, and a power input of 1,500 W was applied to the sputtering electrode 28 using a DC pulse power supply to generate an argon-oxygen gas plasma, thereby forming an SiO2 layer on the surface of the A layer of the substrate 34 by sputtering. The thickness of the formed SiO2 layer was adjusted by the film transport speed. Subsequently, the laminate was obtained by winding it onto the winding roll 32 via guide rolls 29, 30, and 31.

[0090] Next, test specimens were cut from the resulting laminate and various evaluations were performed. The results are shown in Tables 1-3.

[0091] (Example 2) In forming the SnO2+SiO2 layer, which is layer B, a sputtering target sintered with a tin / silicon atomic concentration (atm%) of 50 / 50 was used, and the oxygen gas partial pressure was set to 40%, but otherwise the laminate was obtained in the same manner as in Example 1. The results are shown in Tables 1-3.

[0092] (Example 3) The laminate was obtained in the same manner as in Example 2, except that a sputtering target sintered with a tin / silicon atomic concentration (atm%) of 68 / 32 was used for the formation of the SnO2+SiO2 layer, which is the B layer. The results are shown in Tables 1-3.

[0093] (Example 4) The laminate was obtained in the same manner as in Example 2, except that a sputtering target sintered with a tin / silicon atomic concentration (atm%) of 32 / 68 was used for the formation of the SnO2+SiO2 layer, which is the B layer. The results are shown in Tables 1-3.

[0094] (Example 5) In the formation of the B layer, which is the SnO2+SiO2 layer, a roll-type deposition apparatus shown in Figure 6 was used, and the B layer was formed by electron beam (EB) deposition with a target thickness of 50 nm. Otherwise, the laminate was obtained in the same manner as in Example 1.

[0095] The specific method for forming layer B is as follows. First, granular tin oxide (SnO2, 99.9% purity) and silicon dioxide (SiO2, 99.99% purity) with a size of approximately 2-5 mm were preheated at 100°C for 8 hours as deposition materials. Next, each material was set in a carbon hearth liner 11 as shown in Figure 4. The area ratio of the materials was set to SnO2:SiO2 = 1:1. In the winding chamber 5, the side of the substrate 34 on which layer A is to be applied was set on the unwinding roll 6 so that it faced the hearth liner 11, and the material was unwound and passed through the main drum 10 via guide rolls 7, 8, and 9. At this time, the temperature of the main drum was controlled to -10°C. Next, the pressure inside the deposition apparatus 4 was reduced by a vacuum pump, and 5.0 × 10⁻⁶ -3 A pressure of less than Pa was obtained. Next, an electron gun (hereinafter referred to as EB gun) 13 was used as a heating source, and the heating ratio of MgO and SiO2 was controlled so that the ratio of atomic concentrations (atm%) was approximately Sn:Si = 2:1 for the film composition. The EB gun was set to an acceleration voltage of 10 kV, and the acceleration current and film transport speed were adjusted so that the thickness of the B layer to be formed was approximately 50 nm, and the B layer was formed on the A layer of the substrate 34. After that, it was wound onto a winding roll 18 via guide rolls 15, 16, and 17. The results are shown in Tables 1 to 3.

[0096] (Example 6) The laminate was obtained in the same manner as in Example 2, except that a sputtering target sintered with a zirconium / silicon atomic concentration (atm%) of 33 / 67 was used for the formation of layer B. The results are shown in Tables 1-3.

[0097] (Example 7) As deposition materials, granular zinc oxide (ZnO) with a size of approximately 1-3 mm (99.9% purity) and granular silicon oxide (SiO) with a size of approximately 2-5 mm (99.9% purity) were used. In forming the ZnO+SiO layer, which is layer A, the heating ratio of ZnO and SiO was controlled so that the atomic concentration (atm%) ratio of the film composition ratio was approximately Zn:Si = 1:1. Otherwise, a laminate was obtained in the same manner as in Example 2. The results are shown in Tables 1-3.

[0098] (Example 8) In forming the MgO+SiO2 layer, which is layer A, the heating ratio of MgO and SiO2 was controlled so that the atomic concentration (atm%) ratio was approximately Mg:Si = 1:2, except that the laminate was obtained in the same manner as in Example 2. The results are shown in Tables 1-3.

[0099] (Example 9) A laminate was obtained in the same manner as in Example 2, except that the SnO2+SiO2 layer, which is the B layer of Example 2, was formed as the A layer using the method for forming the B layer, and then the ZrO2+SiO2 layer, which is the B layer of Example 6, was formed as the B layer. The results are shown in Tables 1 to 3.

[0100] (Comparative Example 1) A laminate was obtained in the same manner as in Example 2, except that layer B was not formed after layer A was formed. The results are shown in Tables 1 to 3.

[0101] (Comparative Example 2) A laminate was obtained in the same manner as in Example 7, except that layer B was not formed after layer A was formed. The results are shown in Tables 1 to 3.

[0102] (Comparative Example 3) The laminate was obtained in the same manner as in Example 2, except that a tin sputtering target was used for the formation of layer B. The results are shown in Tables 1-3.

[0103] (Comparative Example 4) A laminate was obtained in the same manner as in Example 1, except that the SiO2 layer, which was layer B in Example 1, was formed as layer A using the method for forming layer B, and then the MgO+SiO2 layer, which was layer A in Example 1, was formed as layer B using the method for forming layer A. The results are shown in Tables 1 to 3.

[0104] Examples 1-6 form a composite oxide film of magnesium oxide and silicon dioxide, exhibiting a gas barrier property of 5.0 × 10⁻⁶. -3 (g / (m 2 The chemical resistance is good, below 24hr·atm. Furthermore, because the B layer is formed of SiO2, SnO+SiO2, or ZrO2+SiO2, it exhibits good chemical resistance.

[0105] As shown in Example 7, even in layers A of different composite oxide films, the gas barrier properties and chemical resistance are good. Furthermore, as shown in Examples 8 and 9, even if the gas barrier properties are slightly inferior to those in Examples 1-6, the presence of layer B ensures good chemical resistance.

[0106] On the other hand, Comparative Examples 1 and 2 exhibit good gas barrier properties but poor chemical resistance. This is because, in both the MgO+SiO2 and ZnO+SiO composite oxide films, layer A disappears upon application of the etching solution. Furthermore, although SnO2 is formed as layer B in Comparative Example 3, the SnO2 film disappears upon application of the etching solution, and layer A also disappears, resulting in poor chemical resistance.

[0107] Furthermore, as in Comparative Example 4, when the order of layers A and B in Example 1 is reversed, the MgO+SiO2 layer, which has poor chemical resistance, is present on the outermost surface, causing layer B (MgO+SiO2 layer) to disappear, resulting in poor chemical resistance.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3] [Industrial applicability]

[0111] The laminate of the present invention exhibits excellent gas barrier properties against oxygen gas, water vapor, etc., and can therefore be usefully used, for example, as packaging material for food and pharmaceuticals, and as a component for electronic devices such as flat-screen televisions and solar cells, but its applications are not limited to these. [Explanation of Symbols]

[0112] 1 Base material 2 A layer 3. Anchor Coat Layer 4. Retractable electron beam (EB) deposition apparatus 5,22 Winding Room 6.23 Unwinding Roll 7,8,9,24,25,26 Winding side guide roll 10.27 Main Drum 11 Hearthliner 12. Vapor deposition materials 13. Electron gun 14 Electron beam 15, 16, 17, 29, 30, 31 Winding side guide roll 18,32 Reel roll 19. Evaporation material B 20 Vapor deposition material C 21. Winding-type sputtering device 28 Sputtering electrode 33 B layer 34 Substrate with layer A formed on its surface

Claims

1. A laminate having, in this order, a composite oxide film A layer (excluding those containing zinc) and a B layer on at least one side of the substrate, wherein the B layer is composed of silicon and oxygen, tin, silicon and oxygen, or zirconium, silicon and oxygen (excluding those where the melting point of the inorganic material in the inorganic material layer provided on at least one side of the substrate is 1500°C or less).

2. The laminate according to claim 1, wherein the A layer and the B layer are composed of different elements or compositional ratios.

3. The laminate according to claim 1 or 2, wherein the A layer has an average lifetime of 0.935 ns or less as measured by the positron beam method.

4. The laminate according to any one of claims 1 to 3, wherein the A layer has a full width at half maximum of the oxygen atom (O1s) peak measured by X-ray photoelectron spectroscopy of 3.25 eV or less.

5. The laminate according to any one of claims 1 to 4, wherein the metallic element of layer A is at least one selected from the group consisting of magnesium and calcium.

6. The laminate according to any one of claims 1 to 5, wherein the A layer comprises magnesium oxide and silicon oxide.

7. The laminate according to any one of claims 1 to 6, wherein the B layer comprises tin oxide and silicon oxide.

8. The laminate according to any one of claims 1 to 7, wherein the A layer has a magnesium (Mg) atom concentration of 5 to 50 (atm%), a silicon (Si) atom concentration of 2 to 30 (atm%), and an oxygen (O) atom concentration of 45 to 70 (atm%) as measured by X-ray photoelectron spectroscopy.

9. The laminate according to any one of claims 1 to 8, wherein the A layer has an atomic concentration (atm%) ratio Mg / (Mg+Si) of magnesium (Mg) atoms to silicon (Si) atoms of 0.45 to 0.

80.

10. The laminate according to any one of claims 1 to 9, wherein the B layer has a tin (Sn) atom concentration of 10 to 30 (atm%), a silicon (Si) atom concentration of 10 to 30 (atm%), and an oxygen (O) atom concentration of 50 to 75 (atm%) as measured by X-ray photoelectron spectroscopy.

11. The method for manufacturing a laminate according to any one of claims 1 to 10, wherein the method for forming the A layer is by vacuum deposition.

12. An organic element sealed in a laminate according to any one of claims 1 to 10.

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