Laminate, film roll, film roll manufacturing method, organic solar cell, and electronic device

Abstract

To provide a laminate which stably exhibits high barrier properties.SOLUTION: A barrier film includes a layer A on a base material film, wherein the layer A contains Mg and Si, when 10 points are collected at an interval of 1 m in a longitudinal direction of the film from a central part in a width direction, and are measured by a transmission electron microscope, standard deviation in the longitudinal direction of the thickness of the layer A is 30 nm or less, and when 10 points are collected at an interval of 1 m in the longitudinal direction of the film from the central part in the width direction, atomic concentrations (atom%) of a Mg atom and an Si atom of the layer A analyzed by X-ray photoelectron spectroscopy are represented by YMg and YSi, where standard deviation in the longitudinal direction of YMg / (YMg+YSi) is 0.055 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate used in components that require high water vapor barrier properties, such as electronic devices. [Background technology]

[0002] Gas barrier films, which are formed by forming an inorganic layer of an inorganic substance (including inorganic oxides) on the surface of a film substrate using physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, or chemical vapor deposition (CVD) methods such as plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition, are used as packaging materials for foods and pharmaceuticals that require blocking various gases such as water vapor and oxygen, and as components for electronic devices such as electronic paper and solar cells. -2 g / m 2 High gas barrier properties of 24hr·atm or less and low-cost manufacturing methods are required.

[0003] As one method for achieving high gas barrier properties, a laminate that has a low cost and simple configuration and high gas barrier properties by mixing two types of elements with oxygen (Patent Document 1) and a laminate that has a simple configuration and high gas barrier properties by adjusting the concentration ratio of silicon and metal elements (Patent Document 2) have been proposed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 080136 [Patent Document 2] Patent Publication No. 2021-169183 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when magnesium compounds are selected as target materials, it is possible to achieve high gas barrier properties by mixing elements with oxygen, as in Patent Document 1. However, magnesium compounds have a high melting point, and therefore require heating with an electron gun when forming a film by vapor deposition. When the electron gun irradiates the target material, the electron beam irradiation position fluctuates in synchronization with the rotation period of the main drum due to magnetic field fluctuations caused by, for example, the rotation of the main drum. As a result, evaporation of the target material is unstable, and depending on the composition, variations in the thickness and element ratio in the film transport direction can occur, resulting in areas where the barrier properties are not exhibited.

[0006] In view of the background of the prior art, an object of the present invention is to provide a laminate that stably exhibits high barrier properties. [Means for solving the problem]

[0007] In order to solve the above problems, a preferred embodiment of the present invention employs the following means. (1) A barrier film comprising a substrate film and an A layer, wherein the A layer contains Mg and Si, and the A layer has a standard deviation in the longitudinal direction of the thickness of 10 points taken at 1 m intervals from the center of the width direction of the film and measured using a transmission electron microscope of 30 nm or less, and the A layer has an atomic concentration (atm%) of Mg atoms and Si atoms analyzed by X-ray photoelectron spectroscopy of 10 points taken at 1 m intervals from the center of the width direction of the film and measured using a transmission electron microscope of 30 nm or less. Mg and Y Si When Y Mg / (Y Mg +Y Si ) in the longitudinal direction is 0.055 or less. (2) The laminate according to (1), wherein the standard deviation of the thickness of the layer A in the longitudinal direction is 5 nm to 20 nm. (3) Y of the A layer Mg / (Y Mg +Y Si ) in the longitudinal direction has a standard deviation of 0.010 to 0.040. (4) The laminate according to any one of (1) to (3), wherein the layer A is amorphous and contains oxides of Mg and Si. (5) The water vapor permeability measured at 40°C and 90% RH is 5.0 x 10 -2 g / m 2 The laminate according to any one of (1) to (4), wherein the drying time is 1 hour or less. (6) The laminate according to any one of (1) to (5), wherein the average thickness of the layer A is 5 nm to 500 nm when measured at 10 points taken at 1 m intervals from the center part in the width direction of the film. (7) Y of layer A when measured at 10 points taken at 1 m intervals from the center of the width direction in the longitudinal direction of the film Mg / (Y Mg +Y Si The laminate according to any one of (1) to (6), wherein the average value of ) is 0.45 to 0.85. (8) A film roll obtained by winding up the laminate according to any one of (1) to (7). (9) A method for producing a film roll by winding up the laminate according to any one of (1) to (7), wherein the layer A is formed by a vapor deposition method using heating by an electron gun. (10) An organic solar cell comprising the laminate according to any one of (1) to (7). (11) An electronic device including the laminate according to any one of (1) to (7). [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a laminate that stably exhibits high barrier properties. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view showing an example of a laminate of the present invention. [Figure 2] FIG. 3 is a cross-sectional view showing another example of the laminate of the present invention. [Figure 3] FIG. 1 is a schematic diagram illustrating an example of a winding-type electron beam vapor deposition apparatus for producing the laminate of the present invention. [Figure 4]FIG. 2 is a diagram schematically illustrating an example of a material arrangement for producing a laminate of the present invention, as viewed from above. [Figure 5] FIG. 1 is a diagram showing a schematic side view of an example of a material arrangement for producing a laminate of the present invention. DETAILED DESCRIPTION OF THE INVENTION

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

[0011] [Laminate] A preferred embodiment of the laminate of the present invention is a barrier film comprising a substrate film and an A layer on the substrate film, the A layer containing Mg and Si, and wherein the A layer has a standard deviation in the longitudinal direction of the thickness of 10 points taken at 1 m intervals from the center of the width direction of the film and measured with a transmission electron microscope of 30 nm or less, and the atomic concentrations (atm%) of Mg atoms and Si atoms of the A layer analyzed by X-ray photoelectron spectroscopy of 10 points taken at 1 m intervals from the center of the width direction of the film and measured are Y Mg and Y Si When Y Mg / (Y Mg +Y Si ) in the longitudinal direction is 0.055 or less.

[0012] From the viewpoints of vapor deposition properties, gas barrier properties, and the formation of a dense structure, Layer A preferably contains magnesium and silicon, and may further contain other metal elements such as calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, germanium, and tin.

[0013] The form of the magnesium and silicon compounds contained in Layer A is not particularly limited and may be oxides, nitrides, oxynitrides, carbides, etc., but from the viewpoints of gas barrier properties, optical properties, etc., they are preferably present in the form of oxides, nitrides, or oxynitrides. From the viewpoints of forming an amorphous film, gas barrier properties, and vapor deposition properties, they are more preferably contained as oxides.

[0014] The laminate of the present invention preferably has a standard deviation in the thickness of Layer A in the longitudinal direction of 30 nm or less when measured using a transmission electron microscope at 10 points taken at 1 m intervals from the center of the width direction of the film. The thickness of Layer A is obtained by evaluation using a transmission electron microscope (TEM), and the specific measurement method is the method described in the Examples. If the standard deviation of the thickness is greater than 30 nm, the stress difference will be strong at locations with large thickness differences, which may make the film more susceptible to cracking and other types of film damage. If the standard deviation of the thickness is 5 nm or less, the thickness will be uniform, making it difficult for stress to be dispersed, and the film may be more susceptible to damage when force is applied to it during winding or subsequent processing. More preferably, the standard deviation is 5 nm or more and 20 nm or less.

[0015] Furthermore, when the thickness of Layer A is measured at 10 points taken at 1 m intervals in the longitudinal direction of the film from the center portion in the width direction, the average thickness is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 100 nm or more. If the thickness is thinner than 5 nm, there will be areas where the layer is not formed, and sufficient gas barrier properties may not be ensured. Furthermore, the thickness of Layer A is preferably 500 nm or less, more preferably 300 nm or less. If the thickness of Layer A is thicker than 500 nm, it may be prone to cracking and its flex resistance and stretchability may be reduced.

[0016] The A layer was analyzed by X-ray photoelectron spectroscopy at 10 points taken at 1 m intervals in the longitudinal direction of the film from the center of the width direction, and the atomic concentration (atm%) of Mg atoms and Si atoms in the A layer was measured. Mg and Y Si When Y Mg / (Y Mg +Y Si) in the longitudinal direction is preferably 0.055 or less, more preferably 0.010 to 0.040, and even more preferably 0.010 to 0.030. If the standard deviation exceeds 0.055, the film may have low density in some areas, impairing its barrier properties and making it difficult to produce a barrier film of consistent quality. Furthermore, if the standard deviation is less than 0.010, the composition ratio is too uniform, resulting in a uniquely determined atomic bonding state, which may make the film more susceptible to cracking due to stress during transportation and winding. The atomic concentration of Layer A is analyzed by X-ray photoelectron spectroscopy (XPS), and the specific measurement method is described in the Examples. Since hydrocarbons and water contained in the air are adsorbed to the outermost surface and do not reflect the true composition of Layer A, the outermost layer is removed by argon ion etching to 5 nm, and the content ratio of each element is measured.

[0017] In addition, the Y value of the layer A when measured at 10 points taken at 1 m intervals from the center of the width direction in the longitudinal direction of the film Mg / (Y Mg +Y Si The average value of Y is preferably 0.45 to 0.85. Mg / (Y Mg +Y Si If Y is less than 0.45, the proportion of silicate bonds in the A layer will be small, resulting in a decrease in density and failure to exhibit gas barrier properties. Mg / (Y Mg +Y Si )>0.85, the A layer is likely to become a crystalline layer and may be prone to cracking. Mg / (Y Mg +Y Si ) is more preferably 0.50 to 0.80, and even more preferably 0.55 to 0.70.

[0018] The atomic concentration (atm%) of oxygen atoms in the layer A analyzed by X-ray photoelectron spectroscopy was expressed as Y O When the Y measured by X-ray photoelectron spectroscopy is Mg is 5 to 50 atm%, Y Si is 2 to 30 atm%, and YO From the viewpoint of film quality and gas barrier properties, Y Mg is 8 to 35 atm%, Y Si is 6 to 25 atm%, and Y O It is more preferable that Y is 50 to 70 atm %. Mg is more than 50atm%, or Y Si If the content of Y is less than 2 atm%, the proportion of silicon element is reduced, which may cause the A layer to become a crystalline layer and cause cracks to occur. Mg is less than 5 atm%, or Y Si If the content of Y is more than 30 atm %, the proportion of silicate bonds in the A layer will be small, which may result in a decrease in density and failure to exhibit gas barrier properties. O If the content is less than 45 atm%, magnesium and silicon may be insufficiently oxidized, resulting in a decrease in light transmittance. O If the content of Y in the A layer is more than 75 atm%, excessive oxygen is taken in, which may increase voids and defects and reduce the gas barrier properties. Mg +Y Si From the viewpoint of stable barrier properties, the content of elements other than Mg, Si, and O is preferably 20 atm% or more and 50 atm% or less, and more preferably 30 atm% or more and 40 atm% or less. From the viewpoint of stable adjustment of element ratios, the content of elements other than Mg, Si, and O is preferably 30 atm% or less, and more preferably 15 atm% or less.

[0019] The laminate of the present invention has a water vapor transmission rate of 5.0×10 measured under conditions of 40°C and 90% RH. -2 g / m 2 From the viewpoint of use as a high-grade packaging material or in electronic device applications where relatively high gas barrier properties are required, the water vapor transmission rate of the laminate of the present invention is preferably 1.0×10 -2 g / m 2 Although there is no particular lower limit to the water vapor transmission rate, if the film becomes too dense, 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 2The water vapor transmission rate is preferably 1 / day or more. The water vapor transmission rate is measured as described in the Examples, and is the average value of measurements of 10 samples.

[0020] The arithmetic mean roughness Ra of the surface of Layer A of the laminate calculated by AFM is preferably 5.0 nm or less. If Ra is greater than 5.0 nm, Layer A will not be dense, and gas barrier properties may not be exhibited. From the viewpoint of gas barrier properties, Ra is preferably 3.0 nm or less, more preferably 2.0 nm or less. Furthermore, the lower limit of Ra is not particularly limited, but is preferably 0.1 nm or more. If Ra is less than 0.1 nm, adhesion may be poor. The analysis range of the AFM when calculating the arithmetic mean roughness Ra is 1 μm × 1 μm.

[0021] Layer A of the laminate preferably has a mean lifetime of 0.935 ns or less as measured by the positron beam method (thin film positron annihilation lifetime measurement method) (see Chapter I, Section 1 and Chapter V, Section 2 of "The Science of Positron Measurement" (Japan Radioisotope Association)). The positron beam method is a positron annihilation lifetime measurement technique that measures the time (on the order of hundreds of ps to tens of ns) from the moment a positron strikes a sample until it annihilates. From the annihilation lifetime, the method nondestructively evaluates information on the size, number concentration, and size distribution of vacancies of approximately 0.1 to 10 nm. This method differs from conventional positron annihilation methods in that it uses a positron beam instead of a radioactive isotope (22Na) as the positron source, enabling it to measure thin films of approximately several hundred nanometers thick deposited on silicon or quartz substrates. The nonlinear least-squares program POSITRONFIT can be used to calculate the mean pore radius and number concentration of pores from the measured values. Sub-nanometer-order pores and basic skeletons can be obtained by analyzing the mean lifetimes of the third and fourth components.

[0022] Here, the third component refers to the average life obtained by selecting an analysis for three components as the measurement conditions for the average life by the positron beam method, and the fourth component refers to the average life obtained by selecting an analysis for four components as the measurement conditions for the average life by the positron beam method. When analyzing using POSITRONFIT, the number of components in POSITRONFIT is determined from the number of peaks obtained in the pore radius distribution curve calculated using the distribution analysis program CONTIN based on the inverse Laplace transform method. The validity of the analysis is determined when the average pore radius calculated by POSITRONFIT and the peak position of the pore radius distribution curve of CONTIN match. The average life in this invention 2 refers to the average life of the third component.

[0023] If the average lifespan is greater than 0.935 ns, the A layer will not be dense enough, and gas barrier properties may not be exhibited. From the viewpoint of gas barrier properties, the average lifespan measured by the positron beam method is preferably 0.912 ns or less, and more preferably 0.863 ns or less. Furthermore, the lower limit of the average lifespan is not particularly limited, but is preferably 0.542 ns or more. If the average lifespan is less than 0.542 ns, flexibility may be reduced.

[0024] To achieve a mean lifetime of 0.935 ns or less as measured by the positron beam method for Layer A, a complex oxide film is densely formed with an appropriate composition ratio on a substrate with an Ra of 3.0 nm or less. "Densely formed" here means that the individual oxides are mixed at the atomic level to form a dense network.

[0025] Layer A of the laminate of the present invention is preferably an amorphous film. Amorphous refers to an irregular structure in which atoms and molecules do not have a long-range, ordered structure like a crystal. A crystalline structure creates grain boundaries, which act as water vapor permeation paths, resulting in poor gas barrier properties and increased cracking. Therefore, an amorphous film is preferred. Whether or not a film is amorphous can be confirmed by analytical methods such as cross-sectional TEM and X-ray diffraction (XRD). In cross-sectional TEM, an amorphous film exhibits uniform contrast and no grain boundaries are visible, whereas a crystalline film exhibits grain boundaries according to the crystal structure, such as a microcrystalline state or a columnar structure.

[0026] The A layer preferably has a silicate bond. A silicate bond is a bond between silicon (Si) and a metal (M) via oxygen (O), and can be expressed as Si-OM. Examples include zinc silicate bond (Si-O-Zn), magnesium silicate bond (Si-O-Mg), and aluminum silicate bond (Si-O-Al). The presence of silicate bonds in the A layer results in a dense structure and high gas barrier properties. Methods for analyzing (confirming) the presence or absence of silicate bonds include X-ray photoelectron spectroscopy and X-ray absorption fine structure (XAFS).

[0027] In order for Layer A to have silicate bonds, as described above, it is preferable that Layer A contains a combination of magnesium and silicon or a combination of zinc and silicon as at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and further contains oxygen.

[0028] The film density of the A layer is 2.0 to 7.0 g / cm from the viewpoint of gas barrier properties and denseness. 3 It is preferable that the density is 2.0 g / cm 3 If the film density of the A layer is smaller than 7.0 g / cm, the resulting A layer will not be dense and sufficient gas barrier properties may not be obtained. 3If the density is larger, the A layer becomes hard and may be prone to cracking or breaking. From the viewpoint of gas barrier properties and ease of breaking, the film density of the A layer is 2.5 to 6.0 g / cm. 3 It is more preferable that:

[0029] In this invention, the film density of Layer A is a value measured by X-ray reflectivity (XRR) ("Introduction to X-ray Reflectivity" (edited by Kenji Sakurai), pp. 51-78). Specifically, X-rays are first generated from an X-ray source and collimated by a multilayer mirror. The X-ray angle is then limited through an entrance slit and incident on the measurement sample. By making the X-ray incident angle on the sample nearly parallel to the sample surface, a shallow angle is formed, generating a reflected X-ray beam that is reflected and interferes with each layer and substrate interface of the sample. The generated reflected beam is then passed through a receiving slit to limit the required X-ray angle, and then incident on a detector to measure the X-ray intensity. Using this method, the total reflection X-ray intensity profile at each incident angle can be obtained by continuously changing the X-ray incident angle.

[0030] The film density of each layer can be analyzed by fitting the measured data of the total reflected X-ray intensity profile against the incident angle of the X-ray to Parratt's theoretical formula using the nonlinear least squares method (see "Introduction to X-ray Reflectivity" (edited by Sakurai Kenji), pp. 81-141).

[0031] The method for forming Layer A is not particularly limited, and methods such as sputtering, vacuum deposition, ion plating, CVD, and atomic layer deposition (ALD) can be used. Among these methods, vacuum deposition is preferred as it is inexpensive, simple, and can achieve the desired properties. In other words, Layer A is preferably formed by vacuum deposition. Among vacuum deposition methods, electron beam (EB) deposition is more preferred from the perspective of depositing a compound and controlling the film composition. Alternatively, reactive vapor deposition may be performed by introducing oxygen, nitrogen, water vapor, or the like as a reactive gas, or by using ion assistance. Furthermore, from the perspective of productivity, a film formation method such as a winding method is preferred for vacuum deposition. Figure 3 shows an example of a winding device.

[0032] [Example of manufacturing method for layer A] An example of a method for forming layer A using a winding-type evaporation system (Figure 3) is shown. A compound thin film of materials B and C is formed as layer A on the surface of substrate 1 by electron beam evaporation. First, materials B and C are alternately arranged as evaporation materials, as shown in Figures 4 and 5. The area ratio of the alternate arrangement is determined based on the target film composition of layer A, the EB irradiation method, and other factors. The width of each material to be arranged is preferably 10 to 100 mm. A width greater than 100 mm is likely to result in large variations in the composition ratio and film quality in the width direction of materials B and C. A width less than 10 mm may reduce workability when arranging the materials. A width of 10 to 80 mm is more preferable from the perspectives of workability, variations in the composition ratio and film quality in the width direction, and workability. The evaporation material may also be in the form of granules or molded bodies such as rectangular or tablet shapes. Using a plate-shaped molded body with a fixed area is particularly preferable, as it can maintain a stable temperature even when the irradiation position fluctuates during electron beam heating. Furthermore, if the deposition material absorbs moisture, the moisture in the material may be incorporated into Layer A, potentially preventing the desired film composition and physical properties from being obtained. Therefore, it is preferable to dehydrate the material by heating before use. In the winding chamber 5, the substrate 1 is set on the unwinding roll 6 so that the side on which Layer A is to be formed faces the hearth liner 11, and then unwound and passed through guide rolls 7, 8, and 9 onto the main drum 10. Materials such as iron and stainless steel are commonly used for the main drum, but stainless steel or iron that has been demagnetized is preferred. Demagnetization reduces or eliminates magnetic bias that occurs in the diameter direction of the main drum, making it less likely for magnetic field fluctuations to occur due to the rotation of the main drum and enabling stable electron beam irradiation. Next, the pressure inside the deposition device 4 is reduced using a vacuum pump, and a pressure of 5.0 × 10 -3 The ultimate vacuum is 5.0×10 Pa or less. -3 The ultimate vacuum is preferably 5.0 x 10 Pa or less. -3If the pressure is higher than Pa, residual gas may be trapped in Layer A, potentially preventing the desired film composition and physical properties from being obtained. The temperature of the main drum 10 is set, for example, to -15°C. To prevent thermal damage to the substrate, a temperature of 20°C or lower is preferred, and 0°C or lower is more preferred. Next, the surfaces of materials B and C were heated using a single electron gun (hereinafter referred to as EB gun) 13 as a heating source. The EB gun was set to an acceleration voltage of 6 kV, an applied current of 50 to 200 mA, and a deposition rate of 1 nm / sec, and Layer A was formed on the surface of the substrate 1 by EB deposition. The thickness of Layer A was adjusted by the film transport speed and applied current, and the film composition ratio was adjusted by the area ratio of materials B and C and the intensity ratio of the applied current. The film was then wound onto a take-up roll 18 via guide rolls 15, 16, and 17.

[0033] In the present invention, the longitudinal direction refers to the direction in which the film is transported, and when evaluating the longitudinal direction, it is preferable to evaluate at least 10 points. In addition, it is preferable to sample at intervals of 10 cm or more in the longitudinal direction.

[0034] [Base material] The substrate used in the present invention is preferably in the form of a film in order to ensure flexibility. The film may be a single-layer film or a film of two or more layers, for example, formed by a co-extrusion method. The type of film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.

[0035] The material of the substrate used in the present invention is not particularly limited, but it is preferable that the substrate is primarily composed of an organic polymer. Examples of organic polymers that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polystyrenes, polyvinyl alcohols, saponified ethylene-vinyl acetate copolymers, polyacrylonitriles, polyacetals, and other polymers. Among these, amorphous cyclic polyolefins or polyethylene terephthalates, which have excellent transparency, versatility, and mechanical properties, are preferred. The organic polymer may be either a homopolymer or a copolymer. A single organic polymer may be used, or multiple organic polymers may be blended.

[0036] The surface of the substrate on which Layer A is formed may be subjected to pretreatment such as corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or treatment to form an anchor coat layer made of an organic or inorganic substance or a mixture thereof in order to improve adhesion and smoothness. Furthermore, a coating layer made of an organic or inorganic substance or a mixture thereof may be laminated on the side opposite to the side on which Layer A is formed in order to improve the slipperiness of the substrate during winding and the scratch resistance of the substrate.

[0037] The thickness of the substrate used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and is preferably 5 μm or more from the viewpoint of ensuring strength against tension and impact. Furthermore, from the viewpoint of ease of processing and handling of the film, the thickness of the substrate is more preferably 10 μm or more and 200 μm or less.

[0038] [Anchor coat layer] The laminate of the present invention preferably has an anchor coat layer, one side of which is in contact with the substrate and the other side of which is in contact with the Layer A. Furthermore, it is more preferable that the anchor coat layer contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. If defects such as protrusions or scratches exist on the substrate, pinholes or cracks may form in the Layer A laminated on the substrate from the defects, impairing the gas barrier properties and flex resistance. Therefore, it is preferable to provide an anchor coat layer. Furthermore, if the difference in thermal dimensional stability between the substrate and Layer A is large, the gas barrier properties and flex resistance may also be reduced, so it is preferable to provide an anchor coat layer. Furthermore, from the viewpoint of thermal dimensional stability and flex resistance, the anchor coat layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure, and more preferably further contains an ethylenically unsaturated compound, a photopolymerization initiator, an organosilicon compound, and / or an inorganic silicon compound.

[0039] The polyurethane compound having an aromatic ring structure used in Layer A of the laminate of the present invention has an aromatic ring and a urethane bond in the main chain or side chain, and can be obtained, for example, by polymerizing an epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule, a diol compound, or a diisocyanate compound.

[0040] Epoxy (meth)acrylates having a hydroxyl group and an aromatic ring in the molecule can be obtained by reacting a diepoxy compound of an aromatic glycol such as bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, resorcinol, or hydroquinone with a (meth)acrylic acid derivative.

[0041] Examples of diol compounds include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexyl methyl ether, and the like. Examples of usable solvents include cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4'-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and bisphenol A. These can be used alone or in combination of two or more.

[0042] Examples of diisocyanate compounds include aromatic diisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4-diphenylmethane diisocyanate; ethylene diisocyanate; hexamethylene diisocyanate; and 2,2,4-trimethylhexamethylene diisocyanate. Examples of the isocyanate include aliphatic diisocyanate compounds such as 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, alicyclic isocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, and methylcyclohexylene diisocyanate, and aromatic aliphatic isocyanate compounds such as xylene diisocyanate and tetramethylxylylene diisocyanate. These can be used alone or in combination of two or more.

[0043] The component ratios of the epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule, the diol compound, and the diisocyanate compound are not particularly limited as long as they are within a range that results in the desired weight-average molecular weight. The weight-average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. A weight-average molecular weight (Mw) of 5,000 to 100,000 is preferred because the resulting cured film has excellent thermal dimensional stability and flex resistance. The weight-average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted into standard polystyrene.

[0044] Examples of ethylenically unsaturated compounds include di(meth)acrylates such as 1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate; polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and epoxy acrylates such as bisphenol A epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate, and bisphenol S epoxy di(meth)acrylate. Among these, polyfunctional (meth)acrylates are preferred because of their excellent thermal dimensional stability and surface protection performance. These compounds may be used as a single composition or as a mixture of two or more components.

[0045] The content of the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, it is preferably in the range of 5 to 90 mass %, and more preferably in the range of 10 to 80 mass %, of the total amount including the polyurethane compound having an aromatic ring structure (100 mass %).

[0046] The photopolymerization initiator is not particularly limited as long as it can maintain the gas barrier properties and flex resistance of the laminate of the present invention. Examples of photopolymerization initiators that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl). alkylphenone-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; titanocene-based photopolymerization initiators such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; and photopolymerization initiators having an oxime ester structure such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)].

[0047] Among these, from the viewpoint of curability and surface protection performance, photopolymerization initiators selected from 1-hydroxy-cyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred. These may be used as a single composition or as a mixture of two or more components.

[0048] 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 parts by mass, and more preferably in the range of 0.1 to 5% by mass, per 100 parts by mass of the total amount of polymerizable components.

[0049] Examples of the organosilicon compound include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatepropyltriethoxysilane.

[0050] Among these, from the viewpoints of curability and polymerization activity upon irradiation with active energy rays, at least one organosilicon compound selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is preferred. These may be used in a single composition or in a mixture of two or more components.

[0051] The content of the organosilicon compound is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of polymerizable components.

[0052] As the inorganic silicon compound, silica particles are preferred from the viewpoints of surface protection performance and transparency, and the primary particle diameter of the silica particles is preferably in the range of 1 to 300 nm, more preferably in the range of 5 to 80 nm. Note that the primary particle diameter here refers to the particle diameter d calculated by applying the specific surface area s calculated by the gas adsorption method to the following formula (1): d=6 / ρs (1) ρ: Density.

[0053] The thickness of the anchor coat layer is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 2,000 nm or less, and even more preferably 500 nm or more and 1,000 nm or less. If the thickness of the anchor coat layer is thinner than 200 nm, the adverse effects of defects such as protrusions and scratches on the substrate may not be suppressed. If the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer decreases, and the unevenness of the surface of Layer A laminated on the anchor coat layer increases. This makes it difficult to achieve a dense vapor-deposited film, which may make it difficult to achieve improved gas barrier properties. The thickness of the anchor coat layer can be measured from cross-sectional images observed using a transmission electron microscope (TEM).

[0054] The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. Setting Ra to 10 nm or less facilitates the formation of a uniform A layer on the anchor coat layer, improving the repeatability and reproducibility of gas barrier properties, which is desirable. If the Ra of the surface of the anchor coat layer exceeds 10 nm, the unevenness of the A layer surface on the anchor coat layer also increases, making it difficult to achieve a dense vapor-deposited film and making it difficult to achieve improved gas barrier properties. Furthermore, cracks are likely to occur due to stress concentration in areas with many unevenness, which may result in a decrease in the repeatability and reproducibility of gas barrier properties. Therefore, in the present invention, the Ra of the anchor coat layer is preferably 10 nm or less, more preferably 5 nm or less. The Ra of the anchor coat layer in the present invention can be measured using an atomic force microscope (AFM) or the like.

[0055] When applying an anchor coat layer to the laminate of the present invention, the preferred means for applying a coating liquid containing a resin that forms the anchor coat layer is to first adjust the solids concentration of a coating material containing a polyurethane compound having an aromatic ring structure onto a substrate so that the thickness after drying is the desired thickness, and then apply the coating material by, for example, reverse coating, gravure coating, rod coating, bar coating, die coating, spray coating, spin coating, etc. In addition, in the present invention, from the viewpoint of coating suitability, it is preferred to dilute the coating material containing a polyurethane compound having an aromatic ring structure with an organic solvent.

[0056] Specifically, it is preferable to dilute the coating material with a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane, or hexane, or an ether solvent such as dibutyl ether, ethyl butyl ether, or tetrahydrofuran to a solids concentration of 10% by mass or less. These solvents may be used alone or in combination. Various additives may also be added to the coating material forming the anchor coat layer as needed. For example, catalysts, antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers, surfactants, leveling agents, antistatic agents, etc. may be used.

[0057] Next, it is preferable to dry the coating film after application to remove the dilution solvent. The heat source used for drying is not particularly limited, and any heat source such as a steam heater, electric heater, or infrared heater can be used. To improve gas barrier properties, the heating temperature is preferably 50 to 150°C. The heat treatment time is preferably several seconds to 1 hour. The temperature may be constant during the heat treatment, or the temperature may be gradually changed. The heat treatment may be performed while adjusting the relative humidity within a range of 20 to 90% RH during the drying treatment. The heat treatment may be performed in the air or while an inert gas is enclosed.

[0058] Next, it is preferable to perform an active energy ray irradiation treatment on the dried coating film containing a polyurethane compound having an aromatic ring structure to crosslink the coating film, thereby forming an anchor coat layer.

[0059] The active energy rays used in such cases are not particularly limited as long as they can cure the anchor coat layer, but ultraviolet treatment is preferred from the perspective of versatility and efficiency. Known sources of ultraviolet light can be used, such as high-pressure mercury lamps, metal halide lamps, microwave electrodeless lamps, low-pressure mercury lamps, and xenon lamps. Furthermore, from the perspective of curing efficiency, active energy rays are preferably used in an inert gas atmosphere such as nitrogen or argon. The ultraviolet treatment may be performed either under atmospheric pressure or under reduced pressure, but from the perspective of versatility and production efficiency, the present invention prefers ultraviolet treatment under atmospheric pressure. Regarding the oxygen concentration during the ultraviolet treatment, the oxygen gas partial pressure is preferably 1.0% or less, more preferably 0.5% or less, from the perspective of controlling the degree of crosslinking of the anchor coat layer. Any relative humidity may be used.

[0060] As the ultraviolet light source, known sources such as a high-pressure mercury lamp, a metal halide lamp, a microwave electrodeless lamp, a low-pressure mercury lamp, and a xenon lamp can be used.

[0061] The cumulative amount of UV light is 0.1 to 1.0 J / cm 2 is preferably 0.2 to 0.6 J / cm 2 It is more preferable that the integrated light amount is 0.1 J / cm. 2 If the integrated light amount is 1.0 J / cm or more, a desired degree of crosslinking of the anchor coat layer can be obtained, which is preferable. 2 If it is less than this, damage to the substrate can be reduced, which is preferable.

[0062] [Other layers] An overcoat layer may be formed on the outermost surface of the laminate of the present invention, i.e., on Layer A, to improve scratch resistance, chemical resistance, printability, etc., to the extent that gas barrier properties are not reduced, or a laminate configuration may be formed in which an adhesive layer or film made of an organic polymer compound is laminated for bonding to elements, etc. Also, a low refractive index layer may be formed to improve optical properties. Note that the outermost surface here refers to the surface of Layer A after Layer A has been laminated on the substrate.

[0063] [Applications of laminates] The laminate of the present invention has high gas barrier properties and can therefore be suitably used as a gas barrier film. The laminate of the present invention can also be used in a variety of electronic devices. For example, the laminate can be suitably used in electronic devices such as solar cells, flexible circuit substrates, organic EL lighting, flexible organic EL displays, and scintillators. Taking advantage of the high barrier properties, the laminate can also be suitably used as an exterior material for lithium ion batteries, packaging materials for pharmaceuticals, and the like. [Example]

[0064] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[0065] [Evaluation method] Sampling was performed on a laminate film roll or a pre-divided film having a length of 10 m or more, by taking 10 samples at 1 m intervals from the center in the width direction along the length of the film.

[0066] (1) The average thickness of each layer measured at 10 points taken at 1 m intervals from the center of the width direction along the length of the film, and the standard deviation of the thickness of layer A along the length Ten samples were taken at 1 m intervals along the longitudinal direction of the film from the center of the width direction. Cross-sectional observation samples were prepared for each sample using a microsampling system (Hitachi, Ltd., FB-2000A) by FIB (specifically, based on the method described in "Polymer Surface Processing Science" (by Akira Iwamori), pp. 118-119). The cross-sections of the samples were observed using a transmission electron microscope (Hitachi, Ltd., H-9000UHRII) at an accelerating voltage of 300 kV. The thicknesses of Layer A and the anchor coat layer of the laminate were measured and the average values ​​were used. The standard deviation of the sample thickness calculated from the data for the 10 Layer A thickness samples was used as the standard deviation of Layer A thickness along the longitudinal direction.

[0067] (2) The composition of layer A (atomic concentration in layer A, Y) at 10 points sampled at 1 m intervals along the longitudinal direction of the film from the center of the width direction Mg / (Y Mg +Y Si )) Ten samples were taken at 1 m intervals along the length of the film from the center of the width direction, and were measured using X-ray photoelectron spectroscopy (XPS) after removing 5 nm of the outermost layer by argon ion etching. Equipment: PHI5000VersaProbe2 (ULVAC-PHI) Excitation X-ray: monochromatic AlKα Analysis range: φ100μm Photoelectron escape angle: 45° Ar ion etching: 3.0 kV, raster size 2 × 2, etching time 1 min.

[0068] Atomic concentration in layer A (Y Mg , Y Si , Y O ) were obtained by analyzing the peak intensities of 2s for magnesium, 2p for silicon, and 1s for oxygen.

[0069] Y Mg / (Y Mg +Y Si ) The sample standard deviation calculated from 10 data points is Y Mg / (Y Mg +Y Si) was taken as the standard deviation in the longitudinal direction.

[0070] (3) Water vapor permeability (g / m 2 / day) The water vapor permeability of the laminate was measured at a temperature of 40°C, humidity of 90% RH, and an area of ​​50 cm 2 Measurements were made under the conditions below using a water vapor transmission rate measuring device (model name: DELTAPERM (registered trademark)) manufactured by Technolox, UK. Ten samples were measured per level. The average value of the data obtained from the measurements of the 10 samples was calculated, and this value was used as the water vapor transmission rate (g / m 2 / day).

[0071] In addition, as an index of the stability of the water vapor transmission rate, the following judgment was made in addition to the average value of the 10 samples.

[0072] A: All 10 samples are 5.0 x 10 -3 g / m 2 / day.

[0073] B: All 10 samples are 1.0 × 10 -2 g / m 2 / day.

[0074] C: All 10 samples are 5.0 × 10 -2 g / m 2 / day.

[0075] D: 5.0 × 10 for at least one sample out of 10 -2 g / m 2 / day or more, 1.0×10 -1 g / m 2 Some are less than / day.

[0076] E: 1.0 x 10 for at least 1 sample out of 10 -1 g / m 2 There's more than / day.

[0077] (4) Evaluation of crack resistance The crack resistance due to stress relaxation of Layer A was evaluated using the following two methods. First, 10 sampled films were stacked in a size of 100 mm x 100 mm, a 1 kg weight was placed on top, and the film was left to stand for 24 hours. The surface of each film was then observed under a microscope to check for the presence of cracks or surface deformation. Additionally, both ends of each of the 10 sampled films were clamped with a clip, a 1 kg weight was attached to one end, and the film was left to stand for 24 hours. The surface of each film was then observed under a microscope to check for the presence of cracks or surface deformation. The following evaluations were made as an index of crack resistance.

[0078] A: There were no abnormalities in the appearance of any of the 10 samples.

[0079] B: No cracks were observed in any of the 10 samples, but one or more samples had stuck together.

[0080] C: None of the 10 samples were stuck, but cracks occurred in 1 to 3 samples. D: Cracks occurred in 4 to 5 samples out of 10.

[0081] E: Cracks occurred in 6 or more samples out of 10.

[0082] Example 1 (Synthesis of Polyurethane Compounds with Aromatic Ring Structures) A 5-liter, four-neck flask was charged with 300 parts by weight of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., product name: Epoxy Ester 3000A) and 710 parts by weight of ethyl acetate, and the flask was heated to an internal temperature of 60°C. 0.2 parts by weight of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by weight of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. After the addition, the reaction was continued for 2 hours, and then 25 parts by weight 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 addition, yielding a polyurethane compound having an aromatic ring structure and a weight-average molecular weight of 20,000.

[0083] (Formation of anchor coat layer) A polyethylene terephthalate film ("Lumirror" (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 100 μm, a width of 1 m and a length of 100 m was used as the substrate.

[0084] The coating liquid for forming the anchor coat layer was prepared by blending 150 parts by weight of the polyurethane compound, 20 parts by weight of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd., trade name: "IRGACURE" (registered trademark) 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicones Co., Ltd., trade name: KBM-503), 170 parts by weight of ethyl acetate, 350 parts by weight of toluene, and 170 parts by weight of cyclohexanone. The coating liquid was then applied to the substrate using a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), dried at 100°C for 1 minute, and then subjected to ultraviolet treatment under the following conditions to form a 1 μm thick anchor coat layer.

[0085] UV treatment equipment: LH10-10Q-G (manufactured by Fusion UV Systems Japan) Inlet gas: N2 (nitrogen inert box) UV source: Microwave electrodeless lamp Accumulated light output: 400mJ / cm 2 Sample temperature control: room temperature.

[0086] (Formation of Layer A) Using the winding type deposition apparatus shown in Figure 3, an MgO+SiO2 layer was formed as layer A on the surface of the anchor coat layer of the substrate by electron beam (EB) deposition.

[0087] The specific procedure is as follows. First, as deposition materials, magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO2 (purity 99.99%) in the form of square plates approximately 5 mm thick and 50 mm on each side were preheated at 100°C for 8 hours. Next, each material was set in a carbon hearth liner 11 as shown in Figure 4. The area ratio of MgO to SiO2 was MgO:SiO2 = 4:1. In the take-up chamber 5, the substrate 1 was set on the unwinding roll 6 so that the side on which Layer A was to be formed (the side on which the anchor coat was formed) faced the hearth liner 11, and was unwound and passed through guide rolls 7, 8, and 9 onto a demagnetized iron main drum 10. The temperature of the main drum was controlled at -15°C. Next, the pressure inside the deposition device 4 was reduced using a vacuum pump, and a 5.0 x 10 -3 A film thickness of 1000 Pa or less was obtained. Next, an electron gun (hereinafter referred to as EB gun) 13 was used as a heating source to heat MgO and SiO2 in a 1:1 ratio. The EB gun was set to an acceleration voltage of 6 kV, an applied current of 50 to 200 mA, and a deposition rate of 1 to 5 nm / sec. Layer A was formed on the surface of the anchor coat layer of the substrate by EB deposition. The thickness of the formed layer A was adjusted by the applied current and film transport speed, and the composition ratio of layer A was adjusted by the material area and heating ratio of MgO and SiO2. The film was then taken up by take-up roll 18 via guide rolls 15, 16, and 17 at a tension of 150 N / m.

[0088] Subsequently, test pieces were cut out from the resulting laminate and various evaluations were carried out. The results are shown in the table.

[0089] Example 2 A laminate was obtained in the same manner as in Example 1, except that granular magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO2 (purity 99.99%) having a size of about 5 mm were used as deposition materials. The results are shown in the table.

[0090] Example 3 A laminate was obtained in the same manner as in Example 1, except that the deposition materials were not heated in advance. The results are shown in the table.

[0091] Example 4 Except for changing the main drum from iron to stainless steel that had not been subjected to demagnetization treatment, a laminate was obtained in the same manner as in Example 1. The results are shown in the table.

[0092] Example 5 A laminate was obtained in the same manner as in Example 1, except that the size of the deposition material was changed to a square plate with a thickness of about 5 mm and a side of 90 mm. The results are shown in the table.

[0093] Example 6 A laminate was obtained in the same manner as in Example 1, except that the main drum was changed from iron to stainless steel that had not been demagnetized, and the size of the deposition material was changed to a square plate with a thickness of about 5 mm and a side length of 90 mm. The results are shown in Table 1.

[0094] Example 7 A laminate was obtained in the same manner as in Example 1, except that the film formation conditions were adjusted with a target thickness of 290 nm for Layer A. The results are shown in the table.

[0095] Example 8 A laminate was obtained in the same manner as in Example 1, except that the film formation conditions were adjusted with a target thickness of 110 nm for Layer A. The results are shown in the table.

[0096] Example 9 Y in the A layer Mg / (Y Mg +Y Si A laminate was obtained in the same manner as in Example 1, except that the film formation conditions were adjusted with a target value of 0.45. The results are shown in the table.

[0097] Example 10 Y in the A layer Mg / (Y Mg +Y Si A laminate was obtained in the same manner as in Example 1, except that the film formation conditions were adjusted with a target value of 0.80. The results are shown in the table.

[0098] (Comparative Example 1) A laminate was obtained in the same manner as in Example 1, except that the main drum was changed to one made of iron that had not been subjected to demagnetization treatment, granular magnesium oxide (MgO) and silicon dioxide (SiO2) with a size of about 2 mm were used as the deposition materials, and neither of the deposition materials was heated in advance. The results are shown in the table.

[0099] (Comparative Example 2) A laminate was obtained in the same manner as in Comparative Example 1, except that the deposition materials used were magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO2 (purity 99.99%) in the form of square plates about 5 mm thick and 50 mm on each side. The results are shown in the table.

[0100] (Comparative Example 3) Except for changing the main drum to one made of stainless steel that had not been subjected to demagnetization treatment, a laminate was obtained in the same manner as in Comparative Example 1. The results are shown in the table.

[0101] High water vapor permeability is stably exhibited even in the longitudinal direction in Examples 1 to 6. Among them, Examples 1, 5, and 6 are very stable because the standard deviation of the Mg element ratio to Si is small, at 0.040 or less.

[0102] On the other hand, in Comparative Examples 1 to 3, the standard deviation of the thickness is 30 nm or more, or the standard deviation of the Mg element ratio to Si is 0.055 or more, and therefore the water vapor transmission rate is unstable in the longitudinal direction.

[0103] [Table 1]

[0104] [Table 2] [Industrial Applicability]

[0105] The laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, and the like, and can therefore be usefully used, for example, as packaging materials for foods, medicines, and the like, and as components for electronic devices such as organic EL televisions and solar cells, but the uses are not limited to these. [Explanation of symbols]

[0106] 1 Base material 2 A layer 3 Anchor coat layer 4. Wind-up electron beam (EB) deposition equipment 5. Winding Room 6 Unwinding roll 7, 8, 9 Unwinding guide roll 10 Main Drum 11 Hearthliner 12 Vapor deposition materials 13 Electron gun 14 Electron beam 15, 16, 17 Winding side guide roll 18 Take-up roll 19 Evaporation material B 20 Evaporation material C

Claims

1. A barrier film comprising an A layer on a substrate film, the A layer containing Mg and Si, wherein the A layer has a standard deviation in the longitudinal direction of the thickness of the A layer when measured by a transmission electron microscope at 10 points taken at 1 m intervals from the center portion in the width direction of the film, and the atomic concentrations (atm %) of the Mg atoms and Si atoms of the A layer when measured by X-ray photoelectron spectroscopy at 10 points taken at 1 m intervals from the center portion in the width direction of the film are Y Ｍｇ and Y Ｓｉ When Y Ｍｇ / (Y Ｍｇ +Y Ｓｉ ) in the longitudinal direction is 0.055 or less.

2. 2. The laminate according to claim 1, wherein the standard deviation of the thickness of the layer A in the longitudinal direction is 5 nm to 20 nm.

3. Y of the A layer Ｍｇ / (Y Ｍｇ +Y Ｓｉ 2. The laminate according to claim 1, wherein the standard deviation of the linearity of the thickness of the laminate in the longitudinal direction is 0.010 to 0.

040.

4. 2. The laminate according to claim 1, wherein the A layer is an amorphous material containing oxides of Mg and Si.

5. The water vapor transmission rate measured under the conditions of 40°C and 90% RH is 5.0 x 10 －２ g / m ２ 2. The laminate according to claim 1, wherein the average particle size is 1 / day or less.

6. 2. The laminate according to claim 1, wherein the average thickness of layer A is 5 nm to 500 nm when measured at 10 points taken at 1 m intervals from the center part in the width direction of the film.

7. The Y value of the layer A when measuring 10 points taken at 1 m intervals from the center of the width direction in the longitudinal direction of the film Ｍｇ / (Y Ｍｇ +Y Ｓｉ 2. The laminate according to claim 1, wherein the average value of σ is 0.45 to 0.

85.

8. A film roll obtained by winding up the laminate according to any one of claims 1 to 7.

9. The method for producing a film roll obtained by winding up the laminate according to any one of claims 1 to 7, wherein the layer A is formed by a vapor deposition method using heating by an electron gun.

10. An organic solar cell comprising the laminate according to any one of claims 1 to 7.

11. An electronic device comprising the laminate according to any one of claims 1 to 7.

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