JP2024167526A - Laminate and solar cell - Google Patents

Abstract

The present invention provides a laminate in which the gas barrier layer contains magnesium, silicon, and oxygen, and in which the progress of crystallization of MgO is suppressed even in an environment in which water is present, and a solar cell using the same.
The laminate has an A layer and a B layer on at least one side of a substrate, the A layer containing magnesium, silicon, and oxygen.
[Selected Figure] Figure 1

Description

The present invention relates to a laminate that requires high gas barrier properties and durability.

In recent years, gas barrier films used as components of electronic devices such as solar cells, electronic paper, and organic EL displays are required to have high gas barrier properties with a water vapor transmission rate of 5.0×10 ⁻² g/m ² /day or less, as well as flexibility. Gas barrier films formed by forming a vapor-deposited layer of an inorganic substance or an inorganic oxide on the surface of a polymer film substrate using a physical vapor deposition method (PVD method) such as vacuum deposition or sputtering achieve high flexibility and gas barrier properties due to the flexibility of the substrate and the high density of the vapor-deposited film.

As a method for achieving higher performance of gas barrier properties and flexibility, a gas barrier film has been proposed in which a ZnO- _SiO2 -based film is formed on a film substrate by sputtering using a target mainly composed of ZnO and _SiO2 (Patent Document 1), and a gas barrier film has been proposed in which an amorphous single film of a composite oxide such as MgO- _SiO2 is formed on a film substrate by vapor deposition using a target mainly composed of MgO and _SiO2 (Patent Document 2).

JP 2013-147710 A JP 2021-169183 A

The high gas barrier properties of the laminate forming the MgO- _SiO2 composite oxide as in Patent Document 2 are realized by the extremely high density due to the formation of an amorphous structure. Therefore, it has been found that depending on the method of use of the gas barrier film, for example, exposure to a high temperature environment with a large amount of water or water vapor for a long time, the gas permeation path may change due to structural changes in the laminate such as fine cracks caused by film quality changes due to MgO crystallization. However, with the above-mentioned configuration (Patent Document 2), depending on the method of use and the environment of use, the above-mentioned change in gas permeation path could not be completely controlled.

In view of the background of the conventional technology, the present invention aims to provide a laminate containing magnesium, silicon, and oxygen in a gas barrier layer, in which the progress of MgO crystallization is suppressed even in an environment in which water is present, and a solar cell using the same.

In order to solve the above problems, the present invention employs the following means. That is, a preferred embodiment of the present invention is as follows.
(1) A laminate having an A layer and a B layer on at least one side of a substrate, the A layer containing magnesium, silicon, and oxygen.
(2) The laminate according to (1), wherein the ratio Mg/(Mg+Si), which is the atomic concentration ratio of magnesium atoms to silicon atoms, in the average composition in the thickness direction of the layer A, is 0.30 to 0.80 atm %.
(3) The laminate according to (1) or (2), wherein the A layer has an average lifetime of 0.935 ns or less as measured by a positron beam method.
(4) The laminate according to any one of (1) to (3), wherein the A layer has a half-width of an oxygen atom (O1s) peak of 3.25 eV or less as measured by X-ray photoelectron spectroscopy.
(5) The laminate according to any one of (1) to (4), wherein the layer B is a polymer film.
(6) The laminate according to (5), wherein the layer B satisfies both (i) and (ii).
(i) Mass density 0.7g/cm ³ or more 1.75g/cm ³ or less
(ii) A thickness of 300 nm or more and 7,000 nm or less. (7) The laminate according to any one of (1) to (6), wherein the layer B contains one or more compounds selected from a polyurethane compound, a polysilazane compound, a polysiloxane compound, an acrylate, a methacrylate, a mixture of an alkoxide and a water-soluble polymer, and a mixture of a polycondensate of an alkoxide and a water-soluble polymer.
(8) The laminate according to any one of (1) to (4), wherein the layer B is an inorganic film.
(9) The laminate according to (8), wherein the layer B is (iii) and (iv).
(iii) Mass density 2.1g/cm ³ or more 7.5g/cm ³ or less
(iv) A thickness of 10 nm or more and 500 nm or less. (10) The laminate according to any one of (1) to (9), wherein the layer B contains one or more elements selected from the group consisting of tin, indium, zinc, aluminum, nickel, chromium, and titanium.
(11) The laminate according to any one of (1) to (10), having a total light transmittance of 85% or more.
(12) The laminate according to any one of (1) to (11), having an average reflectance of 15% or less in the visible light region (380-780 nm).
(13) A solar cell using the laminate according to any one of (1) to (12) as a protective member.

According to the present invention, it is possible to provide a laminate containing magnesium, silicon, and oxygen in the gas barrier layer, in which the progress of crystallization of MgO is suppressed even in an environment in which water is present, and a solar cell using the same. This also makes it possible to provide a laminate that combines high gas barrier properties with high durability.

FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 1 is a schematic diagram showing a winding type electron beam deposition apparatus for producing a laminate of the present invention. FIG. 2 is a schematic diagram showing, from above, the arrangement of materials for producing the laminate of the present invention. FIG. 2 is a schematic diagram showing a side view of a material arrangement for producing a laminate of the present invention. FIG. 1 is a schematic diagram showing a take-up sputtering apparatus for producing a laminate of the present invention. FIG. 11 is a cross-sectional view showing an example of a comparative example.

The details of the present invention are explained below.

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

By adopting this embodiment, it is possible to obtain a laminate that has high gas barrier properties and is excellent at suppressing the progress of MgO crystallization present in the gas barrier film even in an environment where the atmosphere is at high temperature and where there is a large amount of water or water vapor. Details will be described later.

The magnesium and silicon contained in layer A preferably form an amorphous film, and from the viewpoint of gas barrier properties, are preferably contained as at least one compound selected from the group consisting of oxides, nitrides, oxynitrides, and carbides. Among these, it is more preferable that they contain magnesium oxide and silicon oxide.

The term "containing oxygen" in the A layer means that, when evaluated by X-ray photoelectron spectroscopy (XPS), the oxygen atom content is 10.0 atm% or more at the location where argon ion etching is performed from the outermost surface of the A layer to the position where the thickness of the A layer is 1/2, in terms of the converted thickness of the _SiO2 thickness. From the viewpoint of transparency and denseness, the oxygen atom content is preferably 20.0 atm% or more, and more preferably 40.0 atm% or more. The outermost surface of the A layer refers to the surface opposite to the surface where the A layer is closest to the substrate. The term "containing magnesium" in the A layer means that the magnesium atom content is 5.0 atm% or more when evaluated by XPS in the same manner as above. The term "containing silicon" in the A layer means that the silicon atom content is 2.0 atm% or more when evaluated by XPS in the same manner as above. The analysis method of each element in the XPS evaluation is as described in the examples.

The A layer and the B layer of the present invention are defined by the composition obtained by the depth direction analysis of XPS. The layers are removed by argon ion etching at 5 nm from the outermost surface of the laminate in terms of _SiO2 thickness, and the composition is analyzed. The B layer is defined as the period from the starting point to the end point when the measurement point where the magnesium content in the B layer is 1 atm% or more is set as the starting point of removing the layers and repeating argon ion etching and analysis. The A layer is defined as the period from the starting point to the end point when the measurement point where the magnesium content in the A layer is 1 atm% or less is set as the end point when the measurement point where the magnesium content in the B layer is 1 atm% or more is set as the starting point of removing the layers and repeating argon ion etching and analysis. The A layer is defined as the period from the starting point to the end point when the measurement point where the magnesium content in the A layer is 1 atm% or less is set as the starting point of removing the layers and repeating argon ion etching and analysis. For example, when a layer containing magnesium, silicon, and oxygen in a certain composition ratio is formed, and then a layer containing magnesium, silicon, and oxygen in a different composition ratio is formed, the two layers may be combined to form one A layer. In addition, when a magnesium-containing layer is formed on both sides of a magnesium-free layer, the layer containing magnesium that is closest to the substrate is designated as layer A. Similarly, when a magnesium-free layer is formed with a certain composition ratio and then a magnesium-free layer is formed with a different composition ratio, the two layers may be combined to form layer B.

In the present invention, it is preferable to have the substrate, layer A, and layer B in that order. Layer A contains magnesium, silicon, and oxygen to form a dense composite oxide, which can exhibit high gas barrier properties. It is preferable to form layer B on layer A, since this can inhibit the progression of crystallization of MgO present in layer A. If layer A and layer B are interchanged, the desired gas barrier properties and the effect of inhibiting the progression of MgO crystallization may not be obtained.

As long as the A layer and B layer are present in this order from the substrate side, other layers may be present between the substrate and the A layer or on the B layer. For example, an anchor coat layer may be provided between the substrate and the A layer to smooth the substrate. In addition, a wet coat layer or a dry coat layer may be provided on the B layer to further inhibit the progress of MgO crystallization and to impart chemical resistance and scratch resistance, and the B layer may be formed together, or a substrate/A layer/B layer/A layer structure may be used.

From the viewpoint of transparency, the laminate of the present invention preferably has a total light transmittance of 85% or more. When used as a solar cell member, more efficient power generation is possible, so a total light transmittance of 85% or more is preferable. Furthermore, from the viewpoint of visibility, it is preferable that the average reflectance in the visible light region (380-780 nm) is 15% or less. When used as a solar cell member, more efficient power generation is possible, so a mean reflectance in the visible light region (380-780 nm) is 15% or less is preferable.

[Layer A]
The composition of the A layer of the present invention is preferably a laminate having a magnesium (Mg) atomic concentration of 5 to 50 (atm %), a silicon (Si) atomic concentration of 2 to 30 (atm %), and an oxygen (O) atomic concentration of 45 to 70 (atm %).

The composition ratio of layer A can be measured by X-ray photoelectron spectroscopy (XPS). After removing layer B by argon ion etching, layers are 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.

In order to prevent the A layer from becoming a crystalline layer and being susceptible to cracking, it is preferable that the magnesium atomic concentration is 50 atm% or less and/or the silicon atomic concentration is 2 atm% or more.

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

In order to prevent magnesium and silicon from becoming oxygen deficient and reducing light transmittance, it is preferable that the oxygen atomic concentration is 45 atm% or more. In addition, in order to prevent excessive oxygen from being taken in and to prevent an increase in voids and defects, and to exhibit gas barrier properties, it is preferable that the oxygen atomic concentration is 70 atm% or less.

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

In addition, in terms of the atomic concentration (atm%), O/(Mg+Si) is preferably 1.25 to 2.00. From the standpoint of gas barrier properties and optical properties, O/(Mg+Si) is more preferably 1.40 to 1.75.

In the composition of the A layer of the present invention, the atomic concentration (atm%) ratio Mg/(Mg+Si) of magnesium (Mg) atoms to silicon (Si) atoms is preferably 0.30 to 0.80. By having the atomic concentration (atm%) ratio Mg/(Mg+Si) ≧ 0.30, the proportion of silicate bonds in the A layer is sufficient, and the density is improved to exhibit gas barrier properties. By having the atomic concentration (atm%) ratio Mg/(Mg+Si) ≦ 0.80, the presence of crystal parts in the A layer is suppressed, and the tendency for cracks to occur can be suppressed. From the same viewpoint, the atomic concentration (atm%) ratio Mg/(Mg+Si) is more preferably 0.50 to 0.78, and even more preferably 0.55 to 0.76.

The thickness of the A layer in the present invention is determined from the distance from the starting point to the end point. The distance from the starting point to the end point is the thickness in terms of _SiO2 . The thickness of the A layer is preferably 5 nm or more, and preferably 500 nm or less. By having a thickness of 5 nm or more, it is possible to suppress the occurrence of regions that are not formed as a layer, which makes it impossible to ensure gas barrier properties. In addition, by having a thickness of 500 nm or less, it is possible to suppress the occurrence of cracks easily, and it is also possible to improve bending resistance and stretchability. From the above viewpoint, it is more preferable that the thickness of the A layer is 10 nm or more and 300 nm or less.

The A layer of the laminate of the present invention preferably has an average lifetime of 0.935 ns or less as measured by the positron beam method (thin film positron annihilation lifetime measurement method) (see Chapter I, Section 1, and Chapter V, Section 2 of "The Science of Positron Measurement" (Japan Radioisotope Association)). The positron beam method is one of the positron annihilation lifetime measurement methods, and is a method for measuring the time (on the order of several hundred ps to several tens ^of ns) from when a positron is incident on a sample until it annihilates, and for non-destructively evaluating information on the size, number concentration, and size distribution of vacancies of about 0.1 to 10 nm from the annihilation lifetime. The method is significantly different from the usual positron annihilation method in that a positron beam is used as a positron source instead of a radioisotope (22Na), and is a method that enables the measurement of thin films of about several hundred nm thick formed on silicon or quartz substrates. The average pore radius and number concentration of pores can be obtained from the obtained measured values by the nonlinear least squares program POSITRONFIT. The sub-nm order pores and basic skeletons can be obtained by analyzing the average lifetimes of the third and fourth components.

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

If the average lifespan is greater than 0.935 ns, the A layer will not be dense, 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. There is no particular limit to the lower limit of the average lifespan, but it is preferably 0.542 ns or more. If the average lifespan is less than 0.542 ns, flexibility may decrease.

In order to set the average lifetime of layer A to 0.935 ns or less as measured by the positron beam method as specified in the present invention, this can be achieved by densely forming a complex oxide film with an appropriate composition ratio on a substrate having an arithmetic mean roughness Ra of 10.0 nm or less. "Densely formed" here refers to a state in which the individual oxides are mixed at the atomic level to form a dense network.

The A layer of the present invention preferably has a half-width of the oxygen atom (O1s) peak measured by X-ray photoelectron spectroscopy of 3.25 _eV or less. The half-width refers to the peak width when the peak intensity is _Fmax /2, where Fmax is the maximum value of the peak. The narrower the half-width of the O1s peak, the more uniform the bond network structure is formed, and the more likely it is to become a dense film. From the viewpoint of bond uniformity and barrier properties, it is more preferably 3.00 eV or less, and even more preferably 2.75 eV or less. The lower limit is not particularly limited, but is preferably 1.65 eV or more.

The A layer 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 regular order structure like crystals. A crystalline structure is preferable because grain boundaries are generated, which become water vapor permeation paths, resulting in poor gas barrier properties and easy cracking. Whether or not a film is amorphous can be confirmed by analytical methods such as cross-sectional TEM and thin film X-ray diffraction (XRD). In the case of cross-sectional TEM, the contrast is uniform in an amorphous film and grain boundaries are not observed, while in a crystalline film, grain boundaries corresponding to the crystal structure, such as a microcrystalline state or a columnar structure, are observed. In addition, in the case of thin film X-ray diffraction, no peaks are observed in an amorphous film, while diffraction peaks corresponding to the crystal structure are confirmed in a crystalline film. In particular, in MgO crystals, characteristic peaks are confirmed near 2θ = 43° and 62°, and it is possible to detect 002, 022 diffraction peaks, etc. from the positions of these diffraction peaks.

[Example of manufacturing method of layer A]
The method for forming the A layer is not particularly limited, and may be a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, an atomic layer deposition method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like. From the viewpoint of manufacturing cost, gas barrier properties, etc., it is preferable to use a vacuum deposition method. From the viewpoint of compound deposition, it is more preferable to use electron beam (EB) deposition or ion beam assisted deposition (IBAD) among the vacuum deposition methods.

An example of a method for forming the A layer using the winding type vapor deposition apparatus in FIG. 2 is shown. A compound thin film of materials B and C is provided as the A layer on the surface of the substrate 1 by electron beam vapor deposition. First, granular materials B and C having a size of about 2 to 5 mm are arranged as the vapor deposition materials as shown in FIGS. 3 and 4. The vapor deposition material is not limited to granules, and molded bodies having different shapes such as square or tablet shapes may be used. In addition, the vapor deposition source materials are arranged in the width direction of the substrate in FIGS. 3 and 4, but other arrangements such as mixing two materials in one hearth liner or arranging them in the longitudinal direction may be used. In addition, if the vapor deposition material absorbs moisture, the moisture in the material may be taken into the A layer, and the desired film composition and physical properties may not be obtained, so it is preferable to perform a dehydration treatment by heating the material before use. In the winding chamber 5, the surface of the substrate 1 on which the A layer is to be provided is set on the unwinding roll 6 so that it faces the hearth liner 11, and the substrate is unwound and passed through the main drum 10 via guide rolls 7, 8, and 9. Next, the inside of the deposition device 4 is depressurized by a vacuum pump to obtain 5.0×10 ⁻³ Pa or less. The ultimate vacuum is preferably 5.0×10 ⁻³ Pa or less. If the ultimate vacuum is greater than 5.0×10 ⁻³ Pa, residual gas may be taken into the A layer, and the desired film composition and physical properties may not be obtained. The temperature of the main drum 10 is set to −10° C., for example. From the viewpoint of preventing the substrate from being damaged by heat, it is preferably 20° C. or less, more preferably 0° C. or less. Next, using one electron gun (hereinafter, EB gun) 13 as a heating source, the surfaces of materials B and C are heated to obtain the desired film composition ratio. The EB gun has an acceleration voltage of 10 kV, and the acceleration current and film transport speed are adjusted so that the thickness of the A layer to be formed is about 150 nm, and the A layer is formed on the surface of the substrate 1. Thereafter, the substrate is wound on a winding roll 18 via guide rolls 15, 16, and 17.

[B Layer]
Since the A layer has a high gas barrier property due to having a highly dense amorphous film, the gas barrier property may change due to fine cracks that occur when the film structure changes due to film crystallization, etc. Therefore, by forming the B layer, it is expected to have an effect of suppressing the progress of MgO crystallization even in the presence of water or water vapor.

The B layer of the present invention can be an organic film from the viewpoint of suppressing contact with water vapor. When it is a polymer film, (i) the mass density is preferably 0.7 g/cm ³ or more and 1.75 g/cm ³ or less, and (ii) the thickness is preferably 300 nm or more and 7,000 nm or less, more preferably 400 nm or more and 6,000 nm or less, and even more preferably 800 nm or more and 5,000 nm or less. If the mass density is 0.7 g/cm ³ or more, it is preferable because it is easy to form a highly dense B layer, and the effect of suppressing the progress of crystallization of MgO is improved. From the same viewpoint, the mass density is more preferably 1.0 g/cm ³ or more, more preferably 1.1 g/cm ³ or more, and particularly preferably 1.35 or more. If the mass density is less than 0.7 g/cm ³ , the density of the B layer is low, and sufficient suppression of the progress of crystallization may not be obtained. If the mass density is greater than 1.75 g/ ^cm3 , the bonds between the molecules become stronger and cracks are more likely to occur, so that sufficient suppression of the progress of crystallization may not be achieved. The mass density in the present invention can be measured using X-ray reflectometry (XRR). The polymer film refers to a film made of molecules with a molecular weight of 5,000 or more.

When the B layer is formed from a polymer film, the thickness of the B layer is preferably 300 nm or more and 7,000 nm or less. When the thickness of the B layer is thinner than 300 nm, the amount of water or water vapor in contact with the A layer increases, and the progress of crystallization of MgO in the A layer may not be sufficiently suppressed. When the thickness of the B layer is thicker than 7,000 nm, the total light transmittance of the laminate decreases, and when the laminate is incorporated into a device, the conversion efficiency of a solar cell and the visibility of electronic paper and an organic EL display may deteriorate. Here, the thickness of the B layer is similarly determined from the above starting point to the end point. In addition, when the B layer in the present invention is a film made of molecules having a molecular weight of 5,000 or more and an inorganic film described later, it is preferable that the mass density is 0.7 g/cm ³ or more and 1.75 g/cm ³ or less, and the thickness is 300 nm or more and 7,000 nm or less. The more preferred aspects are the same as above.

From the viewpoints of density, transparency, adhesion, etc., the polymer film forming layer B of the laminate of the present invention preferably contains one or more selected from polyurethane compounds, polysilazane compounds, polysiloxane compounds, acrylates, methacrylates, mixtures of alkoxides and water-soluble polymers, and mixtures of polycondensates of alkoxides and water-soluble polymers.

The polyurethane compound used in layer B has an acrylate or 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. An epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule can be obtained by reacting a diepoxy compound of an aromatic glycol such as bisphenol A type, bisphenol F type, resorcin, or hydroquinone with a (meth)acrylic acid derivative. 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 surface protection performance are preferred. These may be used in a single composition or in a mixture of two or more components.

Examples of polysilazane compounds and polysiloxane compounds include perhydropolysilazane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, Dimethylethoxyethynylsilane, diacetoxydimethylsilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, butyldimethoxyvinylsilane, phenyltrimethylsilane, dimethoxymethylphenylsilane silane, phenyltrimethoxysilane, hexyltrimethoxysilane, dimethylethoxyphenylsilane, benzoyloxytrimethylsilane, dimethylethoxy-3-glycidoxypropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, divinylmethylphenylsilane, diacetoxymethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, diethoxy-3-glycidoxypropylmethylsilane, tetraaryl Examples include oxysilane, diarylmethylphenylsilane, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, 1,4-bis(dimethylvinylsilyl)benzene, 1,3-bis(3-acetoxypropyl)tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane, etc. Among these, perhydropolysilazane, which has excellent denseness, is preferred.

Examples of acrylates and methacrylates include hexanediol diacrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, cyanoethyl (mono)acrylate, isobornyl acrylate, octadecyl acrylate, isodecyl acrylate, lauryl acrylate, β-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, dinitrile acrylate, pentafluorophenyl acrylate, nitrophenyl acrylate, 2-phenoxyethyl acrylate, 2,2,2-trifluoromethyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol Examples of suitable acrylates include butyl diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A epoxy diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propylated trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, phenylthioethyl acrylate, naphthyloxyethyl acrylate, Ebecryl™ 130 cyclic diacrylate (CYTEC INDUSTRIES, INC., New Jersey, USA), epoxy acrylate CN120E50 (Sartomer Company, Exton, Pennsylvania, USA), the corresponding methacrylates of the above acrylates, and mixtures thereof. Representative vinyl compounds include vinyl ether, styrene, vinyl naphthylene, and acrylonitrile. Representative alcohols include hexanediol, naphthalenediol, 2-hydroxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and hydroxyethyl methacrylate. Representative vinyl compounds include vinyl ether, styrene, vinyl naphthylene, and acrylonitrile. Representative carboxylic acids include phthalic acid, terephthalic acid, and (meth)acrylic acid. Representative acid anhydrides include phthalic anhydride and glutaric anhydride. Representative acyl halides include hexanedioyl dichloride and succinyl dichloride. Representative thiols include ethylene glycol-bisthioglycolate and phenylthioethyl acrylate. Representative amines include ethylenediamine and hexane 1,6-diamine.

From the viewpoints of reactivity, stability, and cost, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane can be suitably used as the alkoxide, and these may be used alone or in a mixture of two or more kinds. For example, the water-soluble polymer may be a vinyl alcohol-based resin, polyvinylpyrrolidone, starch, or cellulose-based resin, and among them, vinyl alcohol-based resin, which has excellent gas barrier properties, is preferable. Examples of vinyl alcohol-based resins include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and modified polyvinyl alcohol, and these resins may be used alone or in a mixture of two or more kinds. Vinyl alcohol-based resins are generally obtained by saponifying polyvinyl acetate or its copolymers, and may be partially saponified by saponifying a portion of the acetate groups, or may be completely saponified, but a high degree of saponification is preferable.

There are no particular limitations on the means for applying the coating liquid containing the resin that forms the B layer, and it is preferable to adjust the solids concentration so that the paint has a desired thickness after drying, and apply it by a wet coating method such as gravure coating, rod coating, bar coating, die coating, or spray coating, or a dry processing method such as vacuum deposition, plasma CVD, laser CVD, or thermal CVD.

In addition, when the material forming the B layer is an inorganic film, the mass density is preferably 2.1 g/cm ³ or more and 7.5 g/cm ³ or less from the viewpoint of suppressing the progress of MgO crystallization even in the presence of water or water vapor. If the mass density is 2.1 g/cm ³ or more, it is preferable because it is easy to form a highly dense B layer and the effect of suppressing the progress of MgO crystallization is improved. If the mass density is less than 2.1 g/cm ³ , the density of the B layer is low and a coarse and dense film is formed, so that sufficient suppression of the progress of crystallization may not be obtained. Therefore, in the present invention, the mass density of the inorganic film forming the B layer is preferably 2.1 g/cm ³ or more and 7.5 g/cm ³ or less.

The inorganic film of the present invention refers to a film containing an inorganic substance. The inorganic substance may be a simple inorganic substance or an inorganic compound, such as tin, indium, zinc, aluminum, nickel, chromium, and titanium, as well as their oxides, nitrides, and carbides, which may be used alone or in the form of a mixture of two or more types. In other words, it is preferable that the B layer contains one or more elements selected from tin, indium, zinc, aluminum, nickel, chromium, and titanium.

When the B layer is formed from an inorganic film, the thickness is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 400 nm or less, and even more preferably 30 nm or more and 300 nm or less. If the thickness of the B layer is thinner than 10 nm, the amount of water or water vapor in contact with the A layer increases, and the progress of MgO crystallization in the A layer may not be sufficiently suppressed. If the thickness of the B layer is thicker than 500 nm, the flexibility of the laminate decreases and cracks are more likely to occur, and water or water vapor penetrates into the A layer, and the progress of MgO crystallization in the A layer may not be sufficiently suppressed. Here, the thickness of the B layer is determined from the same definition.

The inorganic film forming layer B of the laminate of the present invention is preferably an inorganic substance or an inorganic oxide, and from the viewpoint of denseness, transparency, etc., it preferably contains one or more elements selected from the group consisting of tin, indium, zinc, aluminum, nickel, chromium, and titanium. From the viewpoint of transparency, it is more preferable that layer B used in the present invention is formed mainly from an oxide of the inorganic substance. Note that "mainly composed of an oxide of an inorganic substance" means that 100% by mass of the film contains 80% by mass or more of an oxide of an inorganic substance.

Examples of inorganic oxides include tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide (SnO), indium zinc oxide (IZO), zinc oxide (ZnO), aluminum oxide (Al ₂ O ₃ ), nickel oxide (NiO), chromium oxide (Cr ₂ O ₃ ), and titanium oxide (TiO ₂ ). In addition, when an oxide containing indium oxide as a main component such as ITO is formed by sputtering or the like, an amorphous film is formed, which is a metastable phase. As a means for reducing distortion and grain boundaries of the structure to be formed, a representative method is to increase the crystallinity by performing an annealing treatment. In addition, it is even better if the inorganic oxide is a conductive film. When the inorganic oxide has insulating properties, friction during the film winding process may cause the B layer to become charged, and discharge may cause scratches or pinholes on the surface of the laminate. There is a concern that water or water vapor may pass through the scratches or pinholes, and crystallization of MgO may progress. The surface resistance of the inorganic oxide is preferably 1×10 ⁻⁴ Ω/□ or less.

The mass density in this invention can be measured using X-ray reflectometry (XRR).

There are no particular limitations on the method for forming layer B, which is made from an inorganic substance or an inorganic oxide, and dry processing 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 methods, and wet coating methods such as gravure coating, rod coating, bar coating, die coating, and spray coating can be used.

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

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

The surface of the substrate on which the A layer is formed may be pretreated to improve adhesion and smoothness by corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or treatment to form an anchor coat layer composed of an organic or inorganic substance or a mixture thereof. Also, on the side opposite to the side on which the A layer is formed, a coating layer of an organic or inorganic substance or a mixture thereof may be laminated for the purpose of improving the slipperiness during winding of the substrate and the scratch resistance of the substrate.
The thickness of the substrate used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and is preferably 5 μm or more from the viewpoint of ensuring strength against tension and impact. Furthermore, the thickness of the substrate is more preferably 10 μm or more and 150 μm or less from the viewpoint of ease of processing and handling of the film.

[Anchor coat layer]
The laminate of the present invention has an anchor coat layer, and it is preferable that 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 contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. When defects such as protrusions or scratches exist on the substrate, pinholes or cracks may occur in the A layer laminated on the substrate starting from the defects, which may impair gas barrier properties and bending resistance, so it is preferable to provide an anchor coat layer. In addition, when the difference in thermal dimensional stability between the substrate and the A layer is large, the gas barrier properties and bending resistance may also decrease, so it is preferable to provide an anchor coat layer. In addition, the anchor coat layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and bending resistance, and more preferably contains an ethylenically unsaturated compound, a photopolymerization initiator, an organic silicon compound and/or an inorganic silicon compound.

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

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

Examples of diol compounds include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexa Examples of the compounds that can be used include diphenylmethanol, 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 compounds may be used in a single composition or in a mixture of two or more components.

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 xylylene diisocyanate and tetramethylxylylene diisocyanate. These may be used in a single composition or in a mixture of two or more components.

The ratio of the components of the epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule, the diol compound, and the diisocyanate compound is not particularly limited as long as it is within the range that results in the desired weight average molecular weight. The weight average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. If the weight average molecular weight (Mw) is 5,000 to 100,000, the resulting cured film has excellent thermal dimensional stability and bending resistance, which is preferable. The weight average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted into standard polystyrene.

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

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

There are no particular limitations on the material of the photopolymerization initiator as long as it can maintain the gas barrier properties and flex resistance of the laminate of the present invention. Examples of photopolymerization initiators that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenyl glyoxylic acid methyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl). Examples of such photopolymerization initiators include alkylphenone-based photopolymerization initiators such as -butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, titanocene-based photopolymerization initiators such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, and photopolymerization initiators having an oxime ester structure such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(0-benzoyloxime)], etc.

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 in a single composition or in a mixture of two or more components.

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

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

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

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

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

The thickness of the anchor coat layer is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 2,000 nm or less, and even more preferably 500 nm or more and 1,000 nm or less. If the thickness of the anchor coat layer is thinner than 200 nm, the adverse effects of defects such as protrusions and scratches present on the substrate may not be suppressed. If the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer decreases and the uneven shape of the surface of the A layer laminated on the anchor coat layer also becomes large, making it difficult for the laminated vapor deposition film to become dense, and the effect of improving the gas barrier property may be difficult to obtain. Here, the thickness of the anchor coat layer can be measured from a cross-sectional observation image obtained by a transmission electron microscope (TEM).

The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. When the Ra is 10 nm or less, it is preferable because it is easy to form a homogeneous A layer on the anchor coat layer, and the repeatability and reproducibility of the gas barrier properties is improved. When the Ra of the surface of the anchor coat layer is greater than 10 nm, the uneven shape of the A layer surface on the anchor coat layer also becomes large, the evaporated film is unlikely to become dense, and the effect of improving the gas barrier properties may be difficult to obtain. In addition, cracks due to stress concentration are likely to occur in the parts with many unevenness, which may cause a decrease in the repeatability and reproducibility of the gas barrier properties. Therefore, in the present invention, it is preferable to set the Ra of the anchor coat layer to 10 nm or less, and more preferably 5 nm or less. The Ra of the anchor coat layer in the present invention can be measured by cross-sectional TEM.

When applying an anchor coat layer to the laminate of the present invention, an example of a means for applying a coating liquid containing a resin that forms an anchor coat layer containing a polyurethane compound having an aromatic ring structure is to first adjust the solids concentration of a paint containing a polyurethane compound having an aromatic ring structure on a substrate so that the thickness after drying is the desired thickness, and then preferably apply the paint by, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a die coating method, a spray coating method, or a spin coating method. Also, in the present invention, it is preferable to dilute the paint containing a polyurethane compound having an aromatic ring structure with an organic solvent from the viewpoint of coating suitability.

Specifically, it is preferable to dilute the coating material to a solids concentration of 10% by mass or less using a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane, or hexane, or an ether solvent such as dibutyl ether, ethyl butyl ether, or tetrahydrofuran. These solvents may be used alone or in combination of two or more. In addition, various additives may be blended into the coating material that forms the anchor coat layer as necessary. For example, catalysts, antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers, surfactants, leveling agents, antistatic agents, etc. may be used.

Then, it is preferable to dry the coating film after application to remove the diluting solvent. Here, there is no particular restriction on the heat source used for drying, and any heat source such as a steam heater, an electric heater, or an infrared heater can be used. In order to improve gas barrier properties, it is preferable to perform the heating at a temperature of 50 to 150°C. In addition, it is preferable to perform the heating treatment for a period of several seconds to 1 hour. Furthermore, the temperature may be constant during the heating treatment, or the temperature may be gradually changed. In addition, the heating treatment may be performed while adjusting the humidity in the range of 20 to 90% RH in terms of relative humidity during the drying treatment. The heating treatment may be performed in the air or while an inert gas is enclosed.

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

The active energy rays to be applied in such a case are not particularly limited as long as they can cure the anchor coat layer, but from the viewpoint of versatility and efficiency, it is preferable to use ultraviolet treatment. As the ultraviolet ray generating source, known sources such as high pressure mercury lamps, metal halide lamps, microwave type electrodeless lamps, low pressure mercury lamps, xenon lamps, etc. can be used. In addition, from the viewpoint of curing efficiency, it is preferable to use active energy rays under an inert gas atmosphere such as nitrogen or argon. The ultraviolet treatment may be performed either under atmospheric pressure or under reduced pressure, but from the viewpoint of versatility and production efficiency, it is preferable to perform the ultraviolet treatment under atmospheric pressure in the present invention. Regarding the oxygen concentration during the ultraviolet treatment, from the viewpoint of controlling the degree of crosslinking of the anchor coat layer, the oxygen gas partial pressure is preferably 1.0% or less, more preferably 0.5% or less. The relative humidity may be arbitrary.

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

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

[Other layers]
The laminate of the present invention may be formed with an overcoat layer or a sealing resin layer for the purpose of improving scratch resistance, chemical resistance, printability, etc., within a range in which the gas barrier property and water vapor transmission rate are not reduced, or may have a laminated structure in which an adhesive layer or film made of an organic polymer compound is laminated for bonding to an element, etc. Also, a low refractive index layer may be formed to improve optical properties. In particular, from the viewpoint of transparency and conductivity, a transparent electrode layer can also be used as an electrode for a solar cell or an organic light-emitting element.

If layer B fulfills the above functions, it may also serve as an overcoat layer, sealing resin layer, adhesive layer, and low refractive index layer. The above overcoat layer and sealing resin layer may be formed on either side of the laminate.

[Applications of the laminate]
Since the laminate of the present invention has both high light transmittance and gas barrier properties, it can be suitably used for optical elements such as electronic paper and organic electroluminescence (EL) displays. In addition, it can be suitably used for solar cells and flexible displays described later.

[Solar Cell]
A preferred embodiment of the solar cell of the present invention is a solar cell including the laminate. This embodiment allows the solar cell to have high durability and energy conversion efficiency, and also has excellent appearance quality. In particular, organic solar cells, dye-sensitized solar cells, and perovskite solar cells have low corrosion resistance to water, so it is expected that the use of the laminate of the present invention will provide a higher effect.

[Flexible display]
A preferred embodiment of the flexible display of the present invention is a flexible display using the laminate or optical laminate described above. By using this embodiment, the flexible display can have high durability and excellent appearance quality and color characteristics.

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

[Evaluation method]
(1) Thickness of each layer The thickness analysis of each layer of the laminate was performed by X-ray photoelectron spectroscopy (XPS). Etching and composition analysis were repeated at 5 nm in _SiO2 equivalent thickness from the outermost surface of the laminate. The thickness of the B layer was measured from the starting point to the end point when the measurement point where the magnesium content in the B layer was 1 atm% or more was set as the end point by repeatedly removing layers from the outermost surface of the laminate and repeating argon ion etching and analysis. The thickness of the A layer was measured from the starting point to the end point when the measurement point where the magnesium content in the A layer was 1 atm% or less was set as the end point by repeating argon ion etching and analysis from the measurement point defined as the end point of the B layer. The thickness of the A layer was measured from the starting point to the end point when the measurement point where the magnesium content in the A layer was 1 atm% or less was set as the end point by repeating argon ion etching and analysis from the measurement point defined as the end point of the B layer.

The peaks used in the analysis were 2s for magnesium and 1s for oxygen.

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

(2) Composition of A layer The composition of the A layer of the laminate was analyzed by X-ray photoelectron spectroscopy (XPS). The content ratio of each element was measured at a location where the thickness of the A layer was halved from the outermost surface of the A layer by argon ion etching in terms of _SiO2 . The peaks used in the analysis were 2s for magnesium, 2p for silicon, and 1s for oxygen.

The O1s half width was determined from the peak width when the peak intensity was F _max /2, where F _max is the maximum value of the peak.

The XPS measurement conditions were as follows.
Apparatus: PHI5000VersaProbeII (ULVAC-PHI, Inc.)
・Excitation X-ray: monochromatic AlKα
Analysis range: φ100μm
Photoelectron escape angle: 45°
Ar ion etching: 3.0 kV, raster size 2 × 2.

(3) Water vapor transmission rate The water vapor transmission rate of the laminate was measured using a water vapor transmission rate measuring device (model name: DELTAPERM (registered trademark)) manufactured by Technolox, UK, under the conditions of a temperature of 40°C, a humidity of 90% RH, and a measurement area of 50 ^cm2 . Two samples were measured per level. The data obtained by measuring the two samples were averaged and rounded off to one decimal place, and the value was determined as the water vapor transmission rate (g/ ^m2 /day).

(4) Light transmittance
The total light transmittance was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the JIS K7361 (1997) standard.

(5) Spectral characteristics (spectral reflectance)
The spectral reflectance in the wavelength range of 300 to 800 nm was measured under the following conditions using a spectrophotometer V-670 (manufactured by JASCO Corporation) and an absolute reflectance measurement unit ARSN-733.

Of the obtained data, the average spectral reflectance in the wavelength range of 380 nm to 780 nm was evaluated.
Incident angle: 5° (the perpendicular direction to the sample plane is set to 0°)
・Measurement wavelength: 300nm to 800nm
Band width: 5.0 nm
Data capture interval: 0.5 nm
Scanning speed: 1,000 nm/min

(6) Mass Density The mass density of layer B was calculated using XRR (X-ray reflectivity measurement). The laminate was sampled to 30 mm x 40 mm, fixed to a sample holder, and X-ray reflectivity measurement was performed under the following measurement conditions. In the measurement data, the density value was estimated from the critical angle, and the film thickness value was estimated from the vibration period, and curve fitting was performed using these as initial values to analyze by optimizing each parameter of film thickness and density, and the thickness, density, and structural density index of each region were measured under the following conditions.
Equipment: Rigaku SmartLab
・Analysis software: Rigaku GlobalFit
・Sample size: 30mm x 40mm
・Incidence X-ray wavelength: 0.1541 nm (Cu Kα1 line)
Output: 45kV, 30mA
・Entrance slit size: 0.05mm x 5.0mm
・Light receiving slit size: 0.05 mm x 20.0 mm
Measurement range (θ): 0 to 4.0°
Step (θ): 0.002°

(7) Positron lifetime and pore radius distribution The positron lifetime and pore radius distribution were measured by the positron beam method (thin film positron annihilation lifetime measurement method). The sample to be measured was attached to a 15 mm x 15 mm square Si wafer and degassed in vacuum at room temperature, and then the measurement was performed. The measurement conditions were as follows.
Equipment: Fuji Invac small positron beam generator PALS200A
Positron source: ^22Na -based positron beam Gamma ray detector: _BaF2 scintillator + photomultiplier tube Instrument constant: 255-278ps, 24.55ps/ch
Beam intensity: 1 keV
Measurement depth: 0 to 100 nm (estimated)
Measurement temperature: room temperature Measurement atmosphere: vacuum Measurement count number: about 5,000,000 counts The measurement results were subjected to a three-component analysis using the nonlinear least squares program POSITRONFIT.

(8) Constant temperature and humidity test The test was performed in accordance with the standard JIS C 60068-2-78 (2015). The test conditions are as follows.
Test temperature: 85±2℃
Relative humidity: 85±5% RH
Test time: 250 hours

After the test, the water vapor transmission rate of the samples was measured in the same manner as above, and the change in water vapor transmission rate was evaluated as follows.
⊚: The change in water vapor transmission rate is less than 1.0×10 ^-3 g/m ² /day ◯: The change in water vapor transmission rate is 1.0×10 ^-3 or more and less than 5.0×10 ^-3 g/m ² /day △: The change in water vapor transmission rate is 5.0×10 ^-3 or more and less than 7.5×10 ^-3 g/m ² /day ×: The change in water vapor transmission rate is 7.5×10 ^-3 g/m ² /day or more

The change in water vapor transmission rate was calculated using the following formula.
Change in water vapor transmission rate = (water vapor transmission rate after constant temperature and humidity test) - (water vapor transmission rate before constant temperature and humidity test).

(9) Evaluation of Crystallization Progress The MgO crystallization progress was measured by XRD (X-ray diffraction method). The sample to be measured was attached to a 10 mm x 10 mm square Si non-reversible plate, and the measurement was performed at room temperature and normal pressure. The diffraction peak used in the analysis was the diffraction peak on the 002 plane of the MgO crystal, and the crystallization progress was evaluated based on the presence or absence of the peak. The diffraction peak was evaluated by regarding the signal that can be detected from the signal (S) to noise (N) ratio (S/N) as one peak. The measurement conditions are as follows.
Equipment: Rigaku SmartLab (rotating anticathode type)
・X-ray source: CuKα ray ・Output: 45 kV, 200 mA
Slit system: 2/3°×10mm-sample-0.3mm-0.8mm
Incident vertical divergence prevention solar slit 5°
Solar slit to prevent vertical light dispersion 5°
・Scan method: 2θ/θ continuous scan ・Measurement range (2θ): 5 to 60°
・Scan step: 0.02°
Scan speed: 0.5°/min. The S/N ratio was evaluated as follows.
◎: S/N is less than 2.5 ◯: S/N is 2.5 or more and less than 5.0 ×: S/N is 5.0 or more

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

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

As a coating liquid for forming an anchor coat layer, 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 DPE-6A), 5 parts by mass of 1-hydroxy-cyclohexylphenyl-ketone (manufactured by BASF Japan, trade name: "IRGACURE" (registered trademark) 184), 3 parts by mass of 3-methacryloxypropylmethyldiethoxysilane (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 were blended to prepare a coating liquid. Next, the coating liquid was applied to the substrate with a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, and after drying, ultraviolet treatment was performed under the following conditions to provide an anchor coat layer having a thickness of 1 μm.
Ultraviolet treatment equipment: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: _N2 (nitrogen inert box)
UV source: Microwave electrodeless lamp Accumulated light quantity: 400 mJ/ ^cm2
Sample temperature control: room temperature.

(Formation of Layer A)
Using the winding type deposition apparatus shown in FIG. 2, a MgO+SiO _bilayer was formed as layer A to a target thickness of 200 nm on the surface of the anchor coat layer of the substrate by electron beam (EB) deposition.

The specific operation is as follows. First, as the deposition material, granular magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO ₂ (purity 99.99%) having a size of about 2 to 5 mm were each heated at 100° C. for 8 hours in advance. Then, each material was set in a carbon hearth liner 11 as shown in FIG. 3. The area ratio of the materials was set to MgO:SiO ₂ = 1:1. In the winding chamber 5, the surface of the substrate 1 on which the A layer was to be provided was set on the unwinding roll 6 so as to face the hearth liner 11, and the substrate was unwound and passed through the main drum 10 via the 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 device 4 was reduced by a vacuum pump to obtain a pressure of 5.0×10 ^-3 Pa or less. Next, an electron gun (hereinafter, EB gun) 13 was used as a heating source, and the heating ratio of MgO and _SiO2 was controlled so that the atomic concentration (atm%) ratio of the film was about Mg:Si=2:1. The EB gun had an acceleration voltage of 10 kV, and the acceleration current and film transport speed were adjusted so that the thickness of the A layer to be formed was about 200 nm, forming the A layer on the surface of the substrate 1. Thereafter, the film was wound around the winding roll 18 via guide rolls 15, 16, and 17.

(Formation of layer B containing organic matter)
Following the formation of Layer A, a coating liquid for forming Layer B was prepared by blending 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: "Light Acrylate" (registered trademark) DPE-6A), 5 parts by mass of 1-hydroxy-cyclohexylphenyl-ketone (manufactured by BASF Japan Ltd., product name: "IRGACURE" (registered trademark) 184), 3 parts by mass of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicones Co., Ltd., product 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 liquid was applied onto the substrate using a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), and dried at 100°C for 1 minute. After drying, ultraviolet treatment was performed under the following conditions to provide a 1,500 nm thick layer B on layer A.
Ultraviolet treatment equipment: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: _N2 (nitrogen inert box)
UV source: Microwave electrodeless lamp Accumulated light quantity: 400 mJ/ ^cm2
Sample temperature control: Room temperature

Example 2
A laminate was obtained in the same manner as in Example 1, except that in forming the B layer, the target thickness was set to 4,500 nm.

Example 3
A laminate was obtained in the same manner as in Example 1, except that in forming the B layer, the target thickness was set to 700 nm.

Example 4
On the A layer formed by the above method, a 10% by mass dibutyl ether solution of perhydropolysilazane (PHPS, AQUAMICA NN120-10, catalyst-free type, manufactured by AZ Electronic Materials Co., Ltd.) was applied as the B layer using a wireless bar, dried for 1 minute in an atmosphere of 65°C temperature and 55% RH humidity, and further held for 10 minutes in an atmosphere of 25°C temperature and 10% RH (dew point temperature -8°C) for dehumidification. After dehumidification, a modification treatment was performed under the following conditions to obtain a laminate in the same manner as in Example 1, except that a 750 nm-thick B layer was provided on the A layer.
Modification treatment device: Excimer irradiation device MODEL: MECL-M-1-200 (manufactured by MDCOM)
Wavelength: 172 nm
Lamp filling gas: Xe
Excimer light intensity: 130 mW/ ^cm2 (172 nm)
Stage heating temperature: 70°C
Oxygen concentration in the irradiation device: 1.0%
Excimer irradiation time: 5 sec

(Example 5)
The coating solution prepared by the following procedure was applied to the B layer to a thickness of 1,500 nm by the method described below. Polyvinyl alcohol (hereinafter sometimes abbreviated as PVA, molecular weight 1,700, saponification degree 98.5%) was added to a solvent of water/isopropyl alcohol = 97/3 by mass ratio, and heated and stirred at 90 ° C to obtain a polyvinyl alcohol solution with a solid content of 10 mass %. In addition, a tetraethoxysilane solution was obtained by dropping 13.3 g of 0.02N hydrochloric acid aqueous solution while stirring into a solution mixed with 8.4 g of tetraethoxysilane and 3.3 g of methanol. Furthermore, an ethyl silicate solution was obtained by dropping 5.0 g of 0.06N hydrochloric acid aqueous solution while stirring into a solution mixed with 8.0 g of Ethyl Silicate 48 manufactured by Colcoat Co., Ltd. and 12.0 g of methanol. The tetraethoxysilane solution and the ethyl silicate solution were mixed so that the _SiO2- equivalent solid content mass was 60/40 to obtain an inorganic component solution. Then, the polyvinyl alcohol solution and the inorganic component solution were mixed and stirred so that the _SiO2- equivalent solid content mass ratio of the PVA solid content and the inorganic component solution was 65/35, and diluted with water to obtain a coating liquid with a solid content of 12 mass%. A laminate was obtained in the same manner as in Example 1, except that the obtained coating liquid was applied onto the A layer and dried at 110 ° C. to provide the B layer.

Example 6
Except for forming a B layer containing an inorganic film as the B layer, a laminate was obtained in the same manner as in Example 1. The method for forming the B layer on the A layer is as follows.

(Formation of Layer B Containing Inorganic Substance or Inorganic Oxide)
Following the formation of the A layer, a B layer was provided on the A layer of the substrate 34 using a sputtering device having a structure shown in Fig. 5. A sputtering target made of ITO was connected to a sputtering power supply 28, and sputtering was performed using argon gas and oxygen gas, to provide an ITO layer as the B layer on the A layer of the substrate 34 with a target thickness of 500 nm.

The specific operation is as follows. First, in the winding chamber 22 of the sputtering device 28 in which an ITO sputtering target is installed on the sputtering electrode 28, the side of the substrate 34 on which the B layer is to be provided (the side on which the A layer is formed) is set to face the sputtering electrode 28 on the unwinding roll 23, and the substrate 34 is unwound and passed through the guide rolls 24, 25, and 26 through the main drum 27 whose temperature is controlled to 100° C. Next, the inside of the sputtering device 21 is depressurized by a vacuum pump to obtain a pressure of 2.0×10 ⁻³ Pa or less. Next, argon gas and oxygen gas are introduced with an oxygen gas partial pressure of 10% so that the degree of vacuum becomes 5.0×10 ⁻¹ Pa, and an input power of 1,500 W is applied to the sputtering electrode 28 by a DC pulse power source to generate argon-oxygen gas plasma, and an ITO layer is formed on the surface of the A layer of the substrate 34 by sputtering. The thickness of the ITO layer to be formed is adjusted by the film transport speed. Thereafter, the laminate was passed through guide rolls 29, 30, and 31 and wound around a winding roll 32 to obtain a laminate.

Next, test pieces were cut from the resulting laminate and various evaluations were carried out.

(Example 7)
A laminate was obtained in the same manner as in Example 6, except that the layer B was formed to a target thickness of 250 nm.

(Example 8)
A laminate was obtained in the same manner as in Example 6, except that the layer B was formed to a target thickness of 10 nm.

(Example 9)
A laminate was obtained in the same manner as in Example 6, except that SnO was used as the sputtering target, sputtering was performed with argon gas and oxygen gas, and a SnO layer was provided as layer B with a target thickness of about 250 nm.

Example 10
A laminate was obtained in the same manner as in Example 6, except that ZnO was used as the sputtering target, sputtering was performed with argon gas and oxygen gas, and a ZnO layer was provided as layer B with a target thickness of about 250 nm.

Example 11
A laminate was obtained in the same manner as in Example 6, except that Al ₂ O ₃ was used as the sputtering target, sputtering was performed with argon gas and oxygen gas, and an Al ₂ O ₃ layer was provided as layer B with a target thickness of about 250 nm.

Example 12
A laminate was obtained in the same manner as in Example 6, except that Cr ₂ O ₃ was used as the sputtering target, sputtering was performed with argon gas and oxygen gas, and a Cr ₂ O ₃ layer was provided as the B layer with a target thickness of about 250 nm.

Example 13
A laminate was obtained in the same manner as in Example 6, except that _TiO2 was used as a sputtering target, sputtering was performed with argon gas and oxygen gas, and a _TiO2 layer was provided as layer B with a target thickness of about 250 nm.

(Example 14)
A laminate was obtained in the same manner as in Example 6, except that NiO was used as the sputtering target, sputtering was performed with argon gas and oxygen gas, and a NiO layer was provided as layer B with a target thickness of about 250 nm.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1, except that the layer B was not formed.

(Comparative Example 2)
Using the above polyurethane compound as the coating material, the coating liquid was applied to the surface of the anchor coat layer of the substrate using a microgravure coater to provide a polyurethane compound layer as layer B with a target thickness of 2,000 nm on the surface of the anchor coat layer of the substrate shown in Figure 6.

(Comparative Example 3)
Using ITO as a sputtering target, an ITO layer was formed as layer B with a target thickness of 200 nm on the surface of the anchor coat layer of the substrate shown in FIG. 6 by sputtering with argon gas and oxygen gas.

In Example 1, the B layer forms a film of a polyurethane resin, and the total light transmittance is 89.0% or more, the average spectral reflectance is 14.0% or less, which is good, and the water vapor transmission rate change is also less than 1.0×10 ⁻³ g/m ² /day, which is good. Furthermore, the S/N of the peak of the 002 plane derived from MgO crystals, which is an evaluation of the progress of crystallization, is less than 2.5, which is good. In Example 2, since the film thickness is 1500 nm, the total light transmittance is 86.0% or more, but the average spectral reflectance is 14.0% or less, which is good, and the water vapor transmission rate change is also less than 1.0×10 ⁻³ g/m ² /day, which is good. Furthermore, the S/N of the peak of the 002 plane derived from MgO crystals, which is an evaluation of the progress of crystallization, is less than 2.5, which is good. In addition, in Example 3, the total light transmittance is 90.0% or more and the average spectral reflectance is 14.0% or less, which is good, but since the thickness of the B layer is 735 nm and a thin film, the S/N of the peak of the 002 plane derived from the MgO crystal, which is an evaluation of the progress of crystallization, is 2.5 or more and less than 5.0. The change in water vapor transmission rate is 1.0 x 10 ^-3 or more and less than 5.0 x 10 ^-3 g/m ² /day. In Example 4, the total light transmittance is 89.0% or more and the average spectral reflectance is 14.0% or less, which is good, but since the thickness of the B layer is 750 nm and a thin film, the S/N of the peak of the 002 plane derived from the MgO crystal, which is an evaluation of the progress of crystallization, is 2.5 or more and less than 5.0, but the change in water vapor transmission rate is 1.0 x 10 ^-3 or more and less than 5.0 x 10 ^-3 g/m ² /day. In Example 5, the total light transmittance is 90.0% or more, the average spectral reflectance is 14.0% or less, and the water vapor transmission rate change is also good, less than 1.0×10 ⁻³ g/m ² /day. Furthermore, the S/N of the peak of the 002 plane derived from MgO crystals, which is an evaluation of the progress of crystallization, is less than 2.5, which is good. In Examples 6 and 7, even when the B layer forms an ITO film and has a different thickness, the total light transmittance is 86.0% or more, and the water vapor transmission rate change is also good, less than 1.0×10 ⁻³ g/m ² /day. Furthermore, the S/N of the peak of the 002 plane derived from MgO crystals, which is an evaluation of the progress of crystallization, is less than 2.5, which is good. In Example 8, the total light transmittance is 90.0% or more and the average spectral reflectance is 14.0% or less, which is good, but since the thickness of the B layer is 20 nm and a thin film, the S/N of the peak of the 002 plane derived from the MgO crystal, which is an evaluation of the progress of crystallization, is 2.5 or more and less than 5.0, but the change in water vapor transmission rate is 1.0×10 ⁻³ or more and less than 5.0×10 ⁻³ g/m ² /day. In Examples 9 and 10, the average spectral reflectance is 14.0% or less, which is good, and since the mass density is 5.5 g/cm ³ or more, which is high, the change in water vapor transmission rate is also good, less than 1.0×10 ⁻³ g/m ² /day. Furthermore, the S/N of the peak of the 002 plane derived from the MgO crystal, which is an evaluation of the progress of crystallization, is less than 2.5, which is good. In Examples 11 and 12, the B layer forms an oxide film with excellent corrosion resistance, and the change in water vapor transmission rate is also good, less than 1.0×10 ⁻³ g/m ² /day, as a crystallization growth suppression effect. In Example 13, the total light transmittance is 90.0% or more, the average spectral reflectance is 14.0% or less, and the change in water vapor transmission rate is also good, less than 1.0×10 ⁻³ g/m ² /day. Furthermore, the S/N of the peak of the 002 plane derived from MgO crystal, which is an evaluation of the progress of crystallization, was good, less than 2.5. In Example 14, the B layer forms a NiO film having an oxide film with excellent corrosion resistance, and the decrease in water vapor transmission rate is also good, less than 10%. Furthermore, the S/N ratio of the peak of the 002 plane originating from MgO crystals, which is an evaluation of the progress of crystallization, is less than 2.5, and the change in water vapor transmission rate is also favorable, being less than 1.0×10 ⁻³ g/m ² /day.

Comparative Example 1 has good total light transmittance and average spectral reflectance, but does not have layer B, so the peak S/N of the 002 plane derived from MgO crystals is 5.0 or more, and the crystallization growth inhibition effect is inferior to Examples 1 to 14. Comparative Examples 2 and 3 have good total light transmittance and average spectral reflectance, but does not have layer A, which is a highly dense amorphous film, so the water vapor permeability is inferior to Examples 1 to 14.

The laminate of the present invention is suitable for use in optical elements such as electronic paper and organic electroluminescence (EL) displays, since it has both high light transmittance and gas barrier properties. In addition, it can also be used in solar cells and flexible displays, but the applications are not limited to these.

REFERENCE SIGNS LIST 1 Substrate 2 Layer A 3 Anchor coat layer 4 Wind-up type electron beam (EB) deposition device 5, 22 Wind-up chamber 6, 23 Unwinding roll 7, 8, 9, 24, 25, 26 Unwinding side guide roll 10, 27 Main drum 11 Hearth liner 12 Deposition material 13 Electron gun 14 Electron beam 15, 16, 17, 29, 30, 31 Wind-up side guide roll 18, 32 Wind-up roll 19 Deposition material B
20 Evaporation material C
21: Winding type sputtering device 28: Sputtering electrode 33: B layer 34: Substrate having A layer formed on its surface

Claims (13)

A laminate having an A layer and a B layer on at least one side of a substrate, the A layer containing magnesium, silicon, and oxygen. The laminate according to claim 1, wherein the ratio of the atomic concentrations of magnesium atoms and silicon atoms, Mg/(Mg+Si), in the average composition in the thickness direction of the A layer is 0.30 to 0.80 atm%. 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 a positron beam method. The laminate according to claim 1 or 2, wherein the A layer has a half-width of the oxygen atom (O1s) peak measured by X-ray photoelectron spectroscopy of 3.25 eV or less. The laminate according to claim 1, wherein the B layer is a polymer film. The laminate according to claim 5 , wherein the layer B satisfies both (i) and (ii).
(i) Mass density 0.7g/cm ³ or more 1.75g/cm ³ or less
(ii) a thickness of 300 nm or more and 7,000 nm or less The laminate according to claim 5 or 6, wherein the layer B contains one or more selected from the group consisting of polyurethane compounds, polysilazane compounds, polysiloxane compounds, acrylates, methacrylates, mixtures of alkoxides and water-soluble polymers, and mixtures of polycondensates of alkoxides and water-soluble polymers. The laminate according to claim 1, wherein the B layer is an inorganic film. The laminate according to claim 8, wherein the B layer is (iii) and (iv).
(iii) Mass density 2.1g/cm ³ or more 7.5g/cm ³ or less
(iv) a thickness of 10 nm or more and 500 nm or less The laminate according to claim 8 or 9, wherein the layer B contains at least one element selected from the group consisting of tin, indium, zinc, aluminum, nickel, chromium, and titanium. The laminate according to claim 1 or 2, having a total light transmittance of 85% or more. The laminate according to claim 1 or 2, which has an average reflectance of 15% or less in the visible light region (380-780 nm). A solar cell comprising the laminate according to claim 1 or 2 as a protective member.

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