JP2014159153A - Gas barrier laminated body, and solar battery or display body formed by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminated body which has adequate adhesiveness with an adhesion layer and has superior gas barrier properties.SOLUTION: A gas barrier film is the gas barrier laminated body which has a gas barrier layer formed on at least one face of a substrate. In addition, the gas barrier layer has at least a first layer containing zinc and a second layer containing silicon in this order from the substrate. An adhesion layer containing an epoxy resin composition is laminated on the second layer of the gas barrier layer.

Description

  The present invention relates to a gas barrier laminate for use in food and pharmaceutical packaging applications that require high gas barrier properties, solar cells, touch panels, electronic paper, liquid crystal displays, organic EL displays, organic EL lighting, and other display bodies. Is.

  The surface of the substrate is made of an inorganic material such as aluminum oxide (including inorganic oxides), and a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method or an ion plating method, or a plasma chemical vapor. A gas barrier laminate formed by forming a gas barrier layer made of an inorganic substance by using a chemical vapor deposition method (CVD method) such as a phase growth method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method, Used as a packaging material for foods and pharmaceuticals and solar cells that need to shut off various gases such as oxygen, solar cells, touch panel, electronic paper, liquid crystal display, organic EL display and lighting-related electronic device members such as lighting Yes.

The gas barrier laminate includes, for example, a silicon oxide as a main component and at least one kind of carbon, hydrogen, silicon, and oxygen on a base material by a plasma CVD method using a gas containing an organic silicon compound vapor and oxygen. A gas barrier laminate in which a gas barrier layer made of a compound is formed has been proposed (Patent Document 1). There has also been proposed a gas barrier laminate having a gas barrier layer having a multilayer laminate structure in which an organic layer made of an epoxy compound and an inorganic layer made of a silicon oxide are alternately laminated on a substrate (Patent Document 2).
Further, solar cells and display-related electronic devices are used by adopting a sealing configuration of a gas barrier laminate and an adhesive layer using various adhesives.

JP-A-8-142252 JP 2003-341003 A

  However, gas barrier laminates such as Patent Documents 1 and 2 not only have insufficient gas barrier properties but also have insufficient adhesion to the adhesive layer, which causes peeling, and gas enters from the interface between the adhesive layer and the gas barrier layer. There has been a problem that sealing failure such as failure is likely to occur.

  In view of the problems of the prior art, the present invention aims to provide a gas barrier laminate having improved gas barrier properties and improved adhesion with an adhesive layer and having high sealing performance.

In order to solve this problem, the present invention employs the following configuration. That is,
(1) The substrate has a gas barrier layer on at least one surface, and the gas barrier layer has a first layer containing at least zinc and a second layer containing silicon in this order from the substrate, and the second layer of the gas barrier layer A gas barrier laminate obtained by laminating an adhesive layer containing an epoxy resin composition thereon.

Moreover, it is preferable that the gas barrier laminated body of this invention satisfy | fills the following.
(2) The gas barrier laminate according to (1), wherein the adhesive layer further includes an inorganic composition containing at least one inorganic component.
(3) The gas barrier laminate according to (1) or (2), wherein the first layer of the gas barrier layer is any of the following 1-A layer or 1-B layer.
1-A layer: a layer comprising a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide 1-B layer: a layer comprising a coexisting phase of zinc sulfide and silicon dioxide (4) The first layer of the gas barrier layer is a 1-A layer And the zinc (Zn) atom concentration measured by ICP emission spectroscopy is 20.0 to 40.0 atom%, the silicon (Si) atom concentration is 5.0 to 20.0 atom%, and the aluminum (Al) atom Any one of (1) to (3), characterized in that it is composed of a composition having a concentration of 0.5 to 5.0 atom% and an oxygen (O) atom concentration of 35.0 to 70.0 atom%. A gas barrier laminate according to claim 1.
(5) The first layer of the gas barrier layer is a 1-B layer and has a composition in which the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier laminate according to any one of (1) to (4), wherein
(6) The gas barrier laminate according to any one of (1) to (5), wherein the gas barrier laminate has a configuration in which a base layer is laminated between a base material and a gas barrier layer.

Moreover, this invention provides the solar cell of the following (7) and (8), and the display body of (9).
(7) A solar cell using the gas barrier laminate according to any one of (1) to (6).
(8) A solar cell in which the solar cell according to (7) is any one of a silicon solar cell, a compound solar cell, and an organic solar cell.
(9) A display body using the gas barrier laminate according to any one of (1) to (6).

Furthermore, the present invention also provides the following products as the display body described in (9).
(10) A display device that is any one of a touch panel, electronic paper, a liquid crystal display, an organic EL display, and organic EL illumination using the display body according to (9).

  A gas barrier laminate having good adhesion to the adhesive layer and excellent gas barrier properties can be provided.

It is a schematic diagram which shows an example of the cross section of the gas barrier laminated body of this invention. It is a schematic diagram which shows an example of the cross section of the gas barrier laminated body of this invention.

[Gas barrier laminate]
The gas barrier laminate of the present invention has a gas barrier layer on at least one surface of a base material, and the gas barrier layer has a first layer containing at least zinc and a second layer containing silicon in this order from the base material. An adhesive layer containing an epoxy resin composition is laminated on the second layer.

  The schematic diagram which shows an example of the cross section of the gas barrier laminated body of this invention in FIG. 1 is shown. The gas barrier laminate of the present invention can impart high gas barrier properties by providing the first layer containing zinc among the gas barrier layers laminated on the substrate. By including the epoxy resin composition in the adhesive layer, it is possible to achieve both adhesion and gas barrier properties. Furthermore, by providing the gas barrier layer in contact with the adhesive layer containing the epoxy-based resin composition and providing a second layer containing silicon, it is possible to impart high adhesion to the adhesive layer as well as impart gas barrier properties. The gas barrier laminate is free from sealing defects such as gas intrusion from the interface between the adhesive layer and the gas barrier layer.

[Base material]
Specifically as a base material used for the gas barrier laminated body of this invention, resin, glass, etc. can be mentioned, for example. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, polyimide, polyphenylene sulfide, aramid, polyolefins such as polyethylene and polypropylene, polyvinyl alcohol, polystyrene, polylactic acid, polyvinyl chloride, polycarbonate, Acrylic / methacrylic resins such as polymethyl methacrylate, alicyclic acrylic resins, cycloolefin resins, triacetyl cellulose, ABS, polyvinyl acetate, melamine resins, phenolic resins, polyvinyl chloride, polyvinylidene chloride, etc. Resin containing chlorine element (Cl element), resin containing fluorine element (F element), silicone resin, saponified ethylene vinyl acetate copolymer, polyacrylonitrile, polyacrylic resin Tar, and the like. These resins may be homopolymers, copolymers, that is, single polymers, or may be used by blending a plurality of polymers, or may be mixed and / or copolymerized. Moreover, normal soda glass can be used as glass.

  Further, a plurality of these substrates can be used in combination. For example, a composite substrate such as a substrate in which a resin and glass are combined and a substrate in which two or more kinds of resins are laminated may be used.

  The shape of the substrate may be a film that can be wound up with a thickness of 250 μm or less, or a substrate with a thickness of more than 250 μm.

  From the viewpoint of cost, productivity, handleability, etc., a resin film of 250 μm or less is preferable, more preferably 190 μm or less, still more preferably 150 nm or less, and particularly preferably 100 μm or less. The lower limit of the thickness is not particularly limited, but is a resin film of 5 μm or more, more preferably 10 μm or more from the viewpoint of securing strength against tension or impact.

  When using a resin film as a base material, what was made into the film by unstretching, uniaxial stretching, and biaxial stretching of resin can be applied. Furthermore, a single layer film, a film having two or more layers, for example, a film formed by a coextrusion method, a film stretched in a uniaxial direction or a biaxial direction, and the like may be used. In order to improve adhesion, the substrate surface on the side on which the inorganic compound layer is formed is composed of corona treatment, ion bombardment treatment, solvent treatment, roughening treatment, and organic or inorganic matter or a mixture thereof. A pretreatment such as an anchor coat layer forming treatment may be performed. Also, on the surface opposite to the side on which the inorganic compound layer is formed, the slipperiness during winding of the film is improved, and friction with the inorganic compound layer is reduced when the film is wound after the inorganic compound layer is formed. For the purpose, a coating layer of an organic substance, an inorganic substance, or a mixture thereof may be applied.

  Of these resin films, from the viewpoint of moldability to a substrate, optical properties such as transparency, productivity, etc., polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and mixing with PEN and A copolymerized PET film or polypropylene film can be preferably used.

[Gas barrier layer]
The gas barrier layer of the present invention comprises a first layer containing at least zinc and a second layer containing silicon. The gas barrier layer may have a multilayer laminated structure in which the first layer and the second layer are repeatedly laminated. The gas barrier layer may be disposed on one side of the base material, or if the stress balance on the side opposite to the gas barrier layer side is disrupted and warping or deformation occurs on one side only, both sides of the base material are used for stress adjustment purposes. A gas barrier layer may be provided.

  The thickness of the gas barrier layer of the present invention (total thickness of the first layer and the second layer) is preferably 10 nm or more, and more preferably 50 nm or more. If the thickness of the gas barrier layer is less than 10 nm, there may be a portion where the gas barrier property cannot be sufficiently secured, and there may be a problem that the gas barrier property varies in the plane of the gas barrier layer. Further, the lower limit of the thickness of the gas barrier layer of the present invention (total thickness of the first layer and the second layer) is preferably 2000 nm or less, and more preferably 1000 nm or less. When the thickness of the gas barrier layer is greater than 2000 nm, the stress remaining in the layer increases, so that the gas barrier layer is liable to be cracked by bending or external impact, and the gas barrier property may be lowered with use.

[First layer containing zinc]
In the present invention, a high gas barrier property can be imparted by providing the first layer containing zinc in the gas barrier layer. In the first layer, zinc may be contained as a zinc simple substance or a zinc compound, but it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 80% by mass or more of the entire first layer. It is. The zinc compound here is a composition in which the composition ratio of each element whose components are specified by X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc., which will be described later, is expressed as an integer. Treated as a compound having the formula. For example, depending on the conditions at the time of generation, even when ZnS, ZnO or the like has a composition ratio slightly deviated from the stoichiometric ratio, the above-described mass content is calculated as ZnS or ZnO (the same applies hereinafter). ).

If the first layer contains zinc, the first layer contains oxides, nitrides, sulfides, or mixtures of elements such as Si, Al, Ti, Zr, Sn, In, Nb, Mo, and Ta. May be. For example, a layer having a coexisting phase of [1-A] zinc oxide-silicon dioxide-aluminum oxide (hereinafter abbreviated as [1-A] layer) or [1-B] zinc sulfide can be obtained as a high gas barrier property. And a layer composed of a coexisting phase of silicon dioxide (hereinafter abbreviated as [1-B] layer) are preferably used. (Detailed explanation of each of the [1-A] layer and the [1-B] layer will be given later.)
The method for forming the first layer is not particularly limited. For example, the first layer can be formed by a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or the like. Among these methods, the sputtering method is preferable as a method for forming the first layer easily and inexpensively.

[Layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide: 1-A layer]
As the [1-A] layer suitably used as the first layer of the gas barrier layer of the present invention, a layer composed of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide will be described. The “coexisting phase of zinc oxide-silicon dioxide-aluminum oxide” may be abbreviated as “ZnO—SiO ₂ —Al ₂ O ₃ ”. Also, silicon (SiO ₂₎ dioxide, the generation time of the condition, those slightly deviated from the composition ratio of silicon and oxygen on the left formula (SiO~SiO ₂₎ although it is possible to produce, in this specification It will be expressed as silicon dioxide or SiO ₂ and will be treated as its composition. Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc oxide and aluminum oxide. In this specification, zinc oxide or ZnO is used regardless of the deviation of the composition ratio depending on the conditions at the time of production. These are expressed as aluminum oxide or Al ₂ O ₃ and are treated as their compositions.

  The reason why the gas barrier property is improved by applying the [1-A] layer to the gas barrier laminate of the present invention is that, in the coexisting phase of zinc oxide-silicon dioxide-aluminum oxide, the crystalline component and the dioxide contained in zinc oxide. Presumed that by coexisting with the amorphous component of silicon, the crystal growth of zinc oxide, which tends to produce microcrystals, is suppressed and the particle size is reduced, so that the layer is densified and the permeation of oxygen and water vapor is suppressed. doing.

  In addition, the coexistence of aluminum oxide can suppress the crystal growth more than the coexistence of zinc oxide and silicon dioxide, so it is considered that the gas barrier property deterioration due to the generation of cracks can be suppressed. It is done.

  The composition of the [1-A] layer can be measured by ICP emission spectroscopy as described later. Zn atom concentration measured by ICP emission spectroscopy is 20.0 to 40.0 atom%, Si atom concentration is 5.0 to 20.0 atom%, Al atom concentration is 0.5 to 5.0 atom%, O atom The concentration is preferably 35.0 to 70.0 atom%. When the Zn atom concentration is higher than 40.0 atom% or the Si atom concentration is lower than 5.0 atom%, the oxide that suppresses the crystal growth of zinc oxide is insufficient. Gas barrier properties may not be obtained. When the Zn atom concentration is lower than 20.0 atom% or the Si atom concentration is higher than 20.0 atom%, the amorphous component of silicon dioxide inside the layer increases and the flexibility of the layer decreases, and heat and external In some cases, cracks are likely to occur with respect to the stress from. On the other hand, if the Al atom concentration is higher than 5.0 atom%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that cracks are likely to occur due to heat and external stress. When the Al atom concentration is less than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved. In some cases, cracks are likely to occur due to stress. Further, when the O atom concentration is higher than 70.0 atom%, the amount of defects in the [1-A] layer increases, so that a predetermined gas barrier property may not be obtained. When the O atom concentration is less than 35.0 atom%, the oxidation state of zinc, silicon, and aluminum becomes insufficient, crystal growth cannot be suppressed, and the particle diameter becomes large, so that the gas barrier property may be deteriorated. From this viewpoint, the Zn atom concentration is 25.0 to 35.0 atom%, the Si atom concentration is 10.0 to 15.0 atom%, the Al atom concentration is 1.0 to 3.0 atom%, and the O atom concentration is 50.0. More preferably, it is ˜64.0 atom%.

  The component included in the [1-A] layer is not particularly limited as long as zinc oxide, silicon dioxide, and aluminum oxide are in the above composition and are the main components. For example, Al, Ti, Zr, Sn, In, Nb, A metal oxide formed of Mo, Ta, Pd or the like may be included. Here, the main component means 50% by mass or more of the composition of the [1-A] layer, preferably 60% by mass or more, and more preferably 80% by mass or more.

  Since the composition of the [1-A] layer is formed with the same composition as the mixed sintered material used at the time of forming the layer, by using a mixed sintered material having a composition that matches the composition of the target layer. It is possible to adjust the composition of the [1-A] layer.

The composition analysis of the [1-A] layer uses ICP emission spectrometry to quantitatively analyze each element of zinc, silicon, and aluminum, and the composition of zinc oxide, silicon dioxide, aluminum oxide, and the inorganic oxide contained You can know the ratio. The oxygen atoms are calculated on the assumption that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO ₂ ), and aluminum oxide (Al ₂ O ₃ ), respectively. The ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis. When an inorganic layer or a resin layer is laminated on the [1-A] region, ICP emission spectroscopic analysis can be performed after removing the thickness obtained by the X-ray reflectance method by ion etching or chemical treatment. .

  The method for forming the [1-A] layer on the base material (or on the layer provided on the base material (for example, a base layer described later)) is not particularly limited, and is a mixed firing of zinc oxide, silicon dioxide, and aluminum oxide. Using a binder, it can be formed by vacuum deposition, sputtering, ion plating, or the like. When using a single material of zinc oxide, silicon dioxide, and aluminum oxide, form a film of zinc oxide, silicon dioxide, and aluminum oxide simultaneously from separate vapor deposition sources or sputter electrodes, and mix them to the desired composition. Can be formed. Among these methods, the [1-A] layer forming method used in the present invention is more preferably a sputtering method using a mixed sintered material from the viewpoint of gas barrier properties and composition reproducibility of the formed layer.

[Layer consisting of coexisting phase of zinc sulfide and silicon dioxide: 1-B layer]
A layer composed of a coexisting phase of zinc sulfide and silicon dioxide will be described as a [1-B] layer suitably used as the first layer of the gas barrier layer of the present invention. The “zinc sulfide-silicon dioxide coexisting phase” is sometimes abbreviated as “ZnS—SiO ₂ ”. Further, silicon dioxide (SiO _2), depending on the conditions at the time of generation, those slightly deviated from the composition ratio of silicon and oxygen on the left formula (SiO~SiO ₂₎ although it is possible to produce, in the present specification Is expressed as silicon dioxide or SiO ₂ . Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc sulfide, and in this specification, it is expressed as zinc sulfide or ZnS regardless of the deviation of the composition ratio depending on the conditions at the time of formation. It will be treated as a composition.

  The reason why the gas barrier property is improved by applying the [1-B] layer to the gas barrier laminate of the present invention is that, in the zinc sulfide-silicon dioxide coexisting phase, the crystalline component contained in the zinc sulfide and the amorphous silicon dioxide It is presumed that the coexistence of the fine component suppresses crystal growth of zinc sulfide, which is likely to generate microcrystals, and the particle size is reduced, so that the layer is densified and the permeation of oxygen and water vapor is suppressed. In addition, the zinc sulfide-silicon dioxide coexisting phase containing zinc sulfide with suppressed crystal growth is more flexible than a layer formed only of inorganic oxides or metal oxides. It is considered that cracks hardly occur, and that the [1-B] layer can be applied to suppress a decrease in gas barrier properties due to the generation of cracks.

  The composition of the [1-B] layer is preferably such that the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. If the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is greater than 0.9, there will be insufficient oxide that suppresses crystal growth of zinc sulfide, resulting in an increase in voids and defects, resulting in a predetermined gas barrier property. May not be obtained. Moreover, when the mole fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is less than 0.7, the amorphous component of silicon dioxide inside the [1-B] layer increases and the flexibility of the layer decreases. In some cases, cracks are likely to occur due to heat or external stress. A more preferable range of the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.75 to 0.85.

  The components contained in the [1-B] layer are not particularly limited as long as zinc sulfide and silicon dioxide are in the above composition and are the main components. For example, Al, Ti, Zr, Sn, In, Nb, Mo, Ta In addition, a metal oxide such as Pd may be included. Here, the main component means 50% by mass or more of the composition of the [1-B] layer, preferably 60% by mass or more, and more preferably 80% by mass or more.

  Since the composition of the [1-B] layer is formed with the same composition as the mixed sintered material used at the time of forming the layer, the mixed sintered material having a composition suitable for the purpose is used. It is possible to adjust the composition of the layer.

  In the composition analysis of the [1-B] layer, first, the composition ratio of zinc and silicon is obtained by ICP emission spectroscopic analysis. Based on this value, each element is quantitatively analyzed by using Rutherford backscattering method, and zinc sulfide and dioxide dioxide are analyzed. The composition ratio of silicon and other inorganic oxides contained can be known. The ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis. In Rutherford backscattering method, a charged particle accelerated by a high voltage is irradiated on a sample, and the number of charged particles bounced from the sample and the element are identified and quantified from the energy, and the composition ratio of each element can be known. Note that since the [1-B] layer is a composite layer of sulfide and oxide, analysis by Rutherford backscattering method capable of analyzing the composition ratio of sulfur and oxygen is performed. When an inorganic layer or a resin layer is laminated on the [1-B] layer, the thickness obtained by the X-ray reflectance method is removed by ion etching or chemical treatment, and then ICP emission spectroscopic analysis and Rutherford back It can be analyzed by the scattering method.

  The method for forming the [1-B] layer on the base material (or on the layer provided on the base material (for example, a base layer described later)) is not particularly limited, and a mixed sintered material of zinc sulfide and silicon dioxide is used. It can be formed by vacuum deposition, sputtering, ion plating, or the like. When a single material of zinc sulfide and silicon dioxide is used, it can be formed by simultaneously forming films of zinc sulfide and silicon dioxide from different vapor deposition sources or sputtering electrodes, and mixing them to obtain a desired composition. Among these methods, the [1-B] layer forming method used in the present invention is more preferably a sputtering method using a mixed sintered material from the viewpoint of gas barrier properties and composition reproducibility of the formed layer.

[Second layer containing silicon]
In the present invention, by providing the second layer containing silicon in the gas barrier layer, it is possible to give gas barrier properties and high adhesion to an adhesive layer containing an epoxy resin composition to be described later. The gas barrier laminate is less likely to cause sealing failure such as gas intrusion from the interface between the gas barrier layer and the gas barrier layer. In the second layer, silicon may be contained as a silicon simple substance or a silicon compound, but is preferably 50% by mass or more of the entire second layer, more preferably 60% by mass or more, and further preferably 80% by mass or more. It is. The silicon compound here is a composition in which the composition ratio of each element whose components are specified by X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc., which will be described later, is expressed as an integer. Treated as a compound having the formula. For example, silicon dioxide (SiO _2), by the generation time of the condition, those slightly deviated from the composition ratio of silicon and oxygen on the left formula (SiO~SiO ₂₎ although it is possible to produce, even in such a case , And the mass content is calculated as SiO ₂ (the same applies hereinafter).

  The composition of the second layer preferably includes an oxide of silicon having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0. When the atomic ratio of oxygen atoms to silicon atoms is larger than 2.0, the amount of oxygen atoms contained increases, so that void portions and defect portions increase and the effect of improving gas barrier properties may be poor. In addition, when the atomic ratio of oxygen atoms to silicon atoms is smaller than 1.5, the oxygen atoms decrease and the film quality becomes dense, but the flexibility decreases, and cracks are likely to occur due to heat and external stress. There is a case. A more preferable range of the atomic ratio of oxygen atoms to silicon atoms is 1.7 to 1.9.

  The composition analysis of the second layer can quantitatively analyze the atomic weight of each element by using X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopy, and Rutherford backscattering method according to the composition. In the case where an inorganic layer or a resin layer is laminated on the second layer, it is possible to analyze after removing the thickness obtained by the X-ray reflectance method by ion etching or chemical treatment.

  The thickness of the second layer is preferably 10 nm or more, and more preferably 100 nm or more. When the thickness of the layer is less than 10 nm, there are places where sufficient gas barrier properties cannot be secured, causing problems such as variations in gas barrier properties within the surface of the gas barrier layer, and issues such as variations in adhesion with the adhesive layer. There is a case. The thickness of the second layer is preferably 1000 nm or less, and more preferably 500 nm or less. When the thickness of the layer becomes thicker than 1000 nm, the stress remaining in the layer increases, so that the second layer is likely to crack due to bending or external impact, and the gas barrier property decreases with use or cracks occur. Separation of the adhesive layer from the portion may occur.

  The method for forming the second layer is not particularly limited, and can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (abbreviated as a CVD method), or the like. For example, in the case of the vacuum evaporation method, a method of forming an evaporation material containing an element having a small atomic radius and having a low melting point in an environment with a reduced pressure is preferable. In the case of the sputtering method, a thin film having a dense film quality is formed by surface diffusion of particles forming the thin film. Therefore, the surface of the first layer is reactive with oxygen gas, carbon dioxide gas or the like separately from the plasma for sputtering the target material. A plasma assist sputtering method in which a thin film is formed while assisting with a gas plasma is preferable. In the case of the CVD method, it is preferable to activate a monomer gas of a silicon-based organic compound with high-intensity plasma and form a dense silicon-based thin film layer by a polymerization reaction. Of these methods, the sputtering method or the CVD method is more preferable.

  The silicon-based organic compound is a compound containing silicon in the molecule, for example, silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethylsilane, propoxysilane, Dipropoxysilane, tripropoxysilane, tetrapropoxysilane, dimethyldisiloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetramethyldisiloxane, hexamethyldisiloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, undecamethylcyclohexasiloxane, dimethyl Silazane, trimethyldisilazane, tetramethyldisilazane, hexamethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, decamethylcyclopentasiloxane silazane, such undecapeptide methyl cyclohexasilane La disilazane and the like. Among these, hexamethyldisiloxane and tetraethoxysilane are preferable from the viewpoint of handling.

[Adhesive layer containing epoxy resin composition]
In the present invention, adhesion is improved by providing an adhesive layer containing an epoxy resin composition on the second layer of the gas barrier layer, and sealing such as peeling and gas intrusion from the interface between the adhesive layer and the gas barrier layer is performed. A gas barrier laminate without defects is obtained. The adhesive layer may be laminated on at least a part of the second layer of the gas barrier layer.

  The adhesive layer of the present invention only needs to contain at least one epoxy resin composition, two or more epoxy resin compositions, and other resins within a range that does not impair the effects of the present invention. Ingredients and various additives may be included.

The epoxy resin composition is preferably modified by introducing a functional group into the structure in order to improve adhesion to the gas barrier layer. Functional groups include hydroxyl groups, carboxyl groups, phosphate groups, amino groups, quaternary ammonium bases, sulfonic acid groups, cyano groups and other polar groups, and some of these polar groups are counters such as Na ⁺ and K ⁺ state of having a cation (e.g., -ONa, -COONa, _-SO 3 Na, etc.) polar groups, straight-chain alkyl group, branched alkyl group, a cycloalkyl group, an alkenyl group such as vinyl, allyl, hexenyl, phenyl Aryl groups such as tolyl, xylyl, styryl, naphthyl, biphenyl, aralkyl groups such as benzyl and phenethyl, other aromatic groups including heterocyclic rings such as lactone, oxazole, and imidazole, and ring-opening groups thereof, methoxy, ethoxy, isopropoxy, etc. Alkoxy group, acetoxy group, allyloxycarbonyl benzyloxyca Oxycarbonyl groups such Boniru, isocyanate groups, sulfur-containing elements functional groups such as mercapto sulfide, nitrogen-containing elements functional groups such as ureido, ketimino, like halogen-containing elements functional group such as a fluoroalkyl group.

  The adhesive layer preferably has a crosslinked structure from the viewpoint of gas barrier properties. As for the crosslinked structure, the epoxy resin composition itself may have a crosslinked structure, or another resin component different from the epoxy resin composition described later may have a crosslinked structure. In order to form a crosslinked structure, two or more reactive functional groups are included in the structure of the epoxy resin composition or other resin component, and can be formed by a crosslinking reaction. In addition, you may select what can become a reactive functional group simultaneously among the said functional groups which contribute to the adhesive improvement with a gas barrier layer. Particularly preferred are epoxy groups (including glycidyl groups) or carbon-carbon double bond groups that contribute to the polymerization reaction.

Examples of the carbon-carbon double bond group contributing to the polymerization reaction include, for example, isopropenyl group, isopentenyl group, allyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, methacryl group, acrylamide group, Methacrylamide group, arylidene group, allylidine group, vinyl ether group, or carbon-carbon double bond group with halogen element such as fluorine or chlorine bonded to carbon (for example, vinyl fluoride group, vinylidene fluoride group, vinyl chloride) Group, vinylidene chloride group, etc.), a carbon-carbon double bond group having a substituent having an aromatic ring such as phenyl group or naphthyl group (for example, styryl group), or butadienyl group (for example, CH2). _{= C (R 1) -C (} R 2) = CH-, CH 2 = C (R 1) -C (= CH 2) - (R , _{R 2} is a group having a conjugated polyene structure as H or _CH 3)), and the like. In consideration of the characteristics and productivity required from these, one kind or a mixture of two or more kinds may be used.

  The method for forming the crosslinked structure of the adhesive layer can be obtained by performing a polymerization reaction using the reactive functional group as a reactive site. The polymerization reaction in such a case is referred to as curing in this specification. Examples of the curing method include heat curing and photocuring by irradiation with an active electron beam such as ultraviolet light, visible light, and electron beam (hereinafter referred to as photocuring). In the case of photocuring, an active material is generated and cured by containing an initiator and irradiating it with an active electron beam. Here, an initiator generates active species such as radical species, cation species, and anion species, which are active species that start reaction by absorbing active electron beams such as ultraviolet light, visible light, and electron beams. It is a substance that initiates a chemical reaction.

  The degree of cross-linking structure can be adjusted according to the progress of curing, such that only one type of initiator is contained or two or more types having different absorption wavelength ranges are contained, the irradiation amount of the active electron beam is adjusted, etc. Adjustment is possible by appropriately combining the methods. In particular, the method of adjusting the irradiation amount of the active electron beam is preferably used because it is relatively easy to implement. The method of adjusting the irradiation amount can be controlled relatively easily by changing the conditions (output conditions, etc.) of the irradiation body such as the lamp that irradiates the active electron beam. In addition, the irradiation time can be shortened by changing the irradiation distance between the irradiated body such as the lamp and the non-irradiated body or adjusting the transport speed of the irradiated body when manufacturing the conductive laminate of the present invention. Thus, the integrated dose can be controlled. In addition, when irradiating the active electron beam, it is also effective to use a specific atmosphere in which the oxygen concentration is lowered, such as in an atmosphere substituted with an inert gas such as nitrogen or argon, or in an atmosphere deoxygenated. .

  Other resin components different from the epoxy resin composition contained in the adhesive layer of the present invention include thermoplastic resins, thermosetting resins, photocurable resins, and the like, for example, polyester resins and polycarbonate resins. , Acrylic resins, methacrylic resins, polyamide resins such as nylon and benzoguanamine, ABS resins, polyimide resins, olefin resins such as polyethylene and polypropylene, polystyrene resins, polyvinyl acetate resins, melamine resins, phenolic resins, Examples thereof include resins containing chlorine element (Cl element) such as polyvinyl chloride and polyvinylidene chloride, resins containing fluorine element (F element), silicone resins, and cellulose resins.

  Various additives contained in the adhesive layer of the present invention include, for example, organic and inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation resistance stabilizers, leveling agents, slip activators, charging agents An inhibitor, an ultraviolet absorber, a light stabilizer, a nucleating agent, a dye, a filler, a dispersant, a coupling agent, and the like can be used.

  Among these, it is preferable that the adhesive layer of the present invention further includes an inorganic composition containing at least one inorganic component. By including the inorganic composition, sealing defects such as gas intrusion from the interface between the adhesive layer and the gas barrier layer can be further improved. The inorganic composition contained in the adhesive layer of the present invention may be contained in a dispersed state like particles, or may be contained in a compatible state like additives.

  In the case of particles, the shape is not uniquely limited. For example, a flat shape such as a star shape, a leaf shape or a disk shape, a rhombus shape, a rectangular shape, a needle shape, a confetti shape, an aspheric shape such as an indefinite shape. The shape may be a shape, but preferably a flat shape makes it easier for particles to be aligned in one direction and the particles to be aligned in parallel, so that sealing failure such as gas intrusion from the interface between the adhesive layer and the gas barrier layer Can be improved more. Moreover, the material is not uniquely limited, for example, oxides, nitrides, and sulfides of elements such as Si, Al, Ti, Zr, Zn, Sn, In, Nb, Mo, and Ta (silica, Alumina), complex compounds such as kaolin and talc.

  In the case of additives, organometallic compounds (metal alkoxides, etc.), metal / metal compounds (metal oxides, etc.) and their salts (sulfates, carbonates, etc.) and complexes (coordination complexes with amines, etc.) Examples of materials used for these include alkali metals, alkaline earth metals, and Al.

  As an adhesive layer containing such an epoxy resin composition, those commercially available from various manufacturers such as MORESCO (Molesco Moisture Cut Series), Nagase Sangyo Co., Ltd., Nagase ChemteX Co., Ltd. can be used. .

[Underlayer]
The gas barrier laminate of the present invention preferably has a configuration in which an underlayer is laminated between a base material and a gas barrier layer. By laminating the base layer, a gas barrier laminate having higher gas barrier properties is obtained.

  The thickness of the underlayer of the present invention is preferably 50 nm or more and 10 μm or less. If the thickness is less than 50 nm, the gas barrier property may not be improved due to the influence of the unevenness of the substrate. If it is thicker than 10 μm, the base layer warps due to an increase in the stress of the underlayer, and cracks occur in the gas barrier layer, so that the gas barrier property may be lowered. Note that the thickness of the underlayer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

  Examples of the component of the underlayer include organic or inorganic polymers.

  Examples of the inorganic polymer include inorganic oxides such as silicon oxides such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n. Tetraalkoxysilanes such as butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxy Silane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane , N-octi Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, -Glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane , Trialkoxysilanes such as 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, methyltriacetyloxysilane, methyltriphenoxysilane, etc. A sol-gel coating film formed by hydrolysis / polymerization reaction from an alcohol, water, acid, etc. of the organoalkoxysilane, and a sputter deposition film of silicon oxide can be used.

  Examples of the organic polymer include thermoplastic resins, thermosetting resins, photocurable resins, and the like, for example, polyester resins, polycarbonate resins, acrylic resins, methacrylic resins, polyurethane resins, polyether resins. , Polyepoxy resins, Polyamide resins such as nylon and benzoguanamine, ABS resins, Polyimide resins, Olefin resins such as polyethylene and polypropylene, Polystyrene resins, Polyvinyl acetate resins, Melamine resins, Phenol resins, Polyvinyl chloride And organic polymer compounds such as resins containing chlorine element (Cl element) such as polyvinylidene chloride, resins containing elemental fluorine (F element), silicone resins, cellulose resins, etc. Select at least one type based on characteristics and productivity In addition, two or more of these may be mixed, but is preferably composed of a polymer containing a structure in which a compound having two or more carbon-carbon double bond groups contributing to the polymerization reaction is polymerized. It is preferable that

  Such a polymer comprises a composition comprising a monomer, an oligomer, or a polymer having two or more carbon-carbon double bond groups that contribute to the polymerization reaction, and a carbon-carbon double bond in the carbon-carbon double bond group. It can be obtained by forming a carbon-carbon single bond by carrying out a polymerization reaction as a reaction point.

Examples of the functional group containing a carbon-carbon double bond group include an isopropenyl group, an isopentenyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a methacryl group, an acrylamide group, and a methacrylamide group. , Arylidene group, allylidine group, vinyl ether group, or carbon-carbon double bond group with a halogen element such as fluorine or chlorine bonded (for example, vinyl fluoride group, vinylidene fluoride group, vinyl chloride group, chloride) Vinylidene groups, etc.), carbon-carbon double bond groups in which a substituent having an aromatic ring such as a phenyl group or a naphthyl group is bonded (for example, styryl groups), butadienyl groups (for example, CH ₂ ═C _{(R 1) -C (R 2} ) = CH-, CH 2 = C (R 1) -C (= CH 2) - (R 1, R 2 H or CH ₃₎₎ group having a conjugated polyene structure as, and the like. In consideration of the characteristics and productivity required from these, one kind or a mixture of two or more kinds may be used.

  Examples of the compound having two or more carbon-carbon double bond groups that contribute to the polymerization reaction include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol ethoxytriacrylate, penta Erythritol ethoxytrimethacrylate, pentaerythritol ethoxytetraacrylate, pentaerythritol ethoxytetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pen Methacrylate, Dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, Trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, Trimethylolpropane ethoxytriacrylate, Trimethylolpropane ethoxytrimethacrylate, Ditrimethylolpropane triacrylate, Ditrimethylolpropane triacrylate Methacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, glycerin propoxytriacrylate, glycerin propoxytrimethacrylate, and compounds having a cyclic skeleton such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring in the molecule (for example, , Triac relay・ Trimethacrylate ・ Tetraacrylate ・ Tetramethacrylate ・ Pentaacrylate ・ Pentamethacrylate ・ Hexaacrylate ・ Hexamethacrylate etc.) and compounds obtained by modifying some of these compounds (eg 2-hydroxypropanoic acid modified with 2-hydroxypropanoic acid etc.) Modified pentaerythritol triacrylate, 2-hydroxypropanoic acid modified pentaerythritol trimethacrylate, 2-hydroxypropanoic acid modified pentaerythritol tetraacrylate, 2-hydroxypropanoic acid modified pentaerythritol tetramethacrylate, and a silicone triacrylate having a silicone skeleton introduced, Silicone trimethacrylate, silicone tetraacrylate, silicone tetramethacrylate, silicone paint Acrylate, silicone pentamethacrylate, silicone hexaacrylate, silicone hexamethacrylate, etc.) and other compounds having a vinyl group and / or vinylidene group in the skeleton (for example, urethane triacrylate, urethane trimethacrylate, urethane having a urethane skeleton) Tetraacrylate, urethane tetramethacrylate, urethane pentaacrylate, urethane pentamethacrylate, urethane hexaacrylate, urethane hexamethacrylate, polyether triacrylate with ether skeleton, polyether trimethacrylate, polyether tetraacrylate, polyether tetramethacrylate, polyether penta Acrylate, polyether pentamethacrylate, poly -Tetrahexaacrylate, Polyetherhexamethacrylate, Epoxytriacrylate with epoxy-derived skeleton, Epoxytrimethacrylate, Epoxytetraacrylate, Epoxytetramethacrylate, Epoxypentaacrylate, Epoxypentamethacrylate, Epoxyhexaacrylate, Epoxyhexamethacrylate, Ester skeleton Polyester triacrylate, polyester trimethacrylate, polyester tetraacrylate, polyester tetramethacrylate, polyester pentaacrylate, polyester pentamethacrylate, polyester hexaacrylate, polyester hexamethacrylate, etc.).

  In consideration of applications, required characteristics, productivity, etc., a composition obtained by polymerizing these alone or a mixture of two or more of them or a dimer or more oligomer obtained by copolymerizing two or more Although the composition formed from can be used, it is not specifically limited to these.

  In the present invention, various additives can be added to the underlayer within a range that does not impair the effects of the present invention. Examples of additives include organic and inorganic fine particles, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, antistatic agents, ultraviolet absorbers, light stabilizers, Nucleating agents, dyes, fillers, dispersants, coupling agents and the like can be used.

  The method for forming the underlayer is not particularly limited, but the coating liquid containing the components of the underlayer is adjusted, and cast, spin coat, dip coat, bar coat, spray, blade coat, slit die coat, gravure coat, reverse coat, screen Examples thereof include a method of coating by a general method such as printing, mold coating, printing transfer, and wet coating methods such as inkjet, and then curing and forming the underlayer by a method described later. Among these coating methods, a wet coating method using micro gravure or slit die coating that can form a conductive layer uniformly and with high productivity is preferable.

  Examples of the curing method include curing by heating (hereinafter referred to as “heat curing”) and curing by irradiation with ultraviolet light, visible light, an electron beam or the like (hereinafter referred to as “photocuring”).

  In the case of photocuring, the above-mentioned initiator is contained, and the active species can be generated simultaneously in the entire system by irradiating light in the ultraviolet region, light in the visible region, electron beam, etc. Photocuring is more preferable because it can shorten the time required for curing and further shorten the curing time.

  Usable initiators include, for example, benzophenone series such as benzophenone, hydroxybenzophenone, 4-phenylbenzophenone, benzoin series such as benzyldimethyl ketal, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 2-methyl 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Examples include α-hydroxy ketones such as butanone-1, α-amino ketones, thioxanthones such as isopropylthioxanthone and 2-4-diethylthioxanthone, methylphenylglyoxylate, and the like. Values of maximum absorption wavelength, absorbance, color From the viewpoint of appearance, coloring degree, etc. Thus, one or more of these initiators can be used in combination.

  Such a photopolymerization initiator is commercially available as 1-hydroxy-cyclohexyl-phenyl-ketone IRGACURE184 (manufactured by BASF), 2-methyl 1 [4- (methylthio) phenyl] -2-morpholinopropane-1 IRGACURE907 (manufactured by BASF) as -one, IRGACURE369 (manufactured by BASF) and the like as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Depending on the nature, only one kind or two or more kinds having different absorption wavelength regions can be contained. In addition, when adjusting the irradiation amount of the ultraviolet light, visible light, electron beam, etc., and further irradiating the ultraviolet light, visible light, electron beam, etc., nitrogen, argon, etc. It is also effective to use a specific atmosphere with a low oxygen concentration, such as an atmosphere substituted with an inert gas or an atmosphere deoxygenated, and an underlayer can be formed by appropriately combining these. it can.

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

[Evaluation method]
First, an evaluation method in each example and comparative example will be described. The number of evaluation n was n = 5 and the average value was obtained unless otherwise specified.

(1) Gas Barrier Layer and Underlayer Thickness Samples for cross-section observation using the microsampling system (FB-2000A manufactured by Hitachi, Ltd.) by the FIB method (specifically, “Polymer Surface Processing” (Iwamori) Ii) produced on the basis of the method described on pages 118 to 119). Using a transmission electron microscope (H-9000UHRII, manufactured by Hitachi, Ltd.), the cross section of the observation sample was observed at an acceleration voltage of 300 kV, and the thicknesses of the first layer, the second layer, and the base layer of the cass barrier layer were measured. .

(2) Water vapor transmission rate Using a water vapor transmission rate measuring device (model name: DELTAPERRM (registered trademark)) manufactured by Technolox, England, under conditions of a temperature of 40 ° C., a humidity of 90% RH, and a measurement area of 50 cm ^2. And measured. The number of samples was 2 samples per level, the number of measurements was 10 for each sample, and the average value was the water vapor transmission rate.

(3) Composition of [1-A] layer The composition analysis of the [1-A] layer was performed by ICP emission spectroscopic analysis (manufactured by SII Nanotechnology, SPS4000). The contents of zinc atom, silicon atom, and aluminum atom in the sample were measured and converted to the atomic ratio. The oxygen atoms were calculated values based on the assumption that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO ₂ ), and aluminum oxide (Al ₂ O ₃ ), respectively.

(4) Composition of [1-B] layer The composition analysis of the [1-B] layer was performed by ICP emission spectroscopic analysis (manufactured by Seiko Denshi Kogyo Co., Ltd., SPS4000), and further based on this value, Rutherford backscattering method Each element was quantitatively analyzed using (Nisshin High Voltage Co., Ltd. AN-2500) to determine the composition ratio of zinc sulfide and silicon dioxide. (5) First layer ([1-A] layer, [ 1-B]), the composition of the second layer The first layer uses an X-ray photoelectron spectroscopy (XPS method) to measure the atomic ratio of the contained metal or nonmetal atom to the oxygen atom, and Accordingly, the above measurements (3) and / or (4) were also used.

For the second layer, the atomic ratio of oxygen atoms to silicon atoms (O / Si ratio) was measured by using X-ray photoelectron spectroscopy (XPS method).
The measurement conditions were as follows.
・ Device: Quantera SXM (manufactured by PHI)
Excitation X-ray: monochromic AlKα1,2
・ X-ray diameter 100μm
-Photoescape angle: 10 °
(6) Adhesiveness of adhesive layer A cross-cut tape peeling test was performed in accordance with JIS K5600-5-6 (1999). First, 100 squares of notches of 1 × 1 mm in 10 × 10 mm were formed in the adhesive layer as a test surface. Subsequently, after using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.) to adhere to the test surface on the adhesive layer with the abdomen of the sticking finger, it was peeled off in the 90 ° direction. Judgment judged that the number of squares in which the adhesive layer does not peel out of 100 squares was 70 to 100 squares, and that there was adhesion. The case of less than 70 squares was rejected and judged as having no adhesion.

Example 1
(Formation of first layer containing zinc)
As a base material, a polyethylene terephthalate film (trade name: “Lumirror” (registered trademark) U48) manufactured by Toray Industries, Inc.) having a thickness of 50 μm, and a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide A sputtering target (composition mass ratio = zinc oxide / silicon dioxide / aluminum oxide = 77.0 / 20.0 / 3.0) was prepared.

Next, the sputtering target is sputtered using a chemical vapor deposition apparatus (hereinafter abbreviated as sputtering / CVD apparatus), and the oxygen gas partial pressure is 10% so that the degree of vacuum is 2 × 10 ⁻¹ Pa. Then, an argon / oxygen gas plasma is generated by applying an input power of 500 W from a DC power source, and the [1-A] layer is 150 nm as the first layer containing zinc on one side of the substrate by sputtering. Formed. The composition of the first layer, ZnO is 71.2 wt%, _Al 2 _{O 3} is 3.7 wt%, SiO ₂ is 25.0 wt%, the total content of ZnO and _Al 2 _{O 3} is 74 It was 9 mass%.

(Formation of second layer containing silicon)
Using hexamethyldisiloxane as a raw material, using the sputtering / CVD apparatus as the raw material, introducing oxygen gas 0.5 L / min and hexamethyldisiloxane 70 cc / min so that the degree of vacuum is 2 × 10 ⁻¹ Pa, Plasma was generated by applying an input power of 500 W to the CVD electrode from a high frequency power source, and a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
As a raw material for the adhesive layer containing an epoxy resin composition, Moresco Moisture Cut WB90US (MORESCO) containing a flat inorganic composition was prepared. Next, after applying the raw material on the second layer, the metal halide lamp is irradiated with ultraviolet rays at ² J / cm ² to be cured, and then heated at 80 ° C. for 1 hour to be post-cured to include a flat inorganic composition. An adhesive layer having a crosslinked structure and having a thickness of 100 μm was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. The composition of the first layer of the gas barrier layer in the gas barrier laminate of this example is as follows: Zn atom concentration is 27.5 atom%, Si atom concentration is 13.1 atom%, Al atom concentration is 2.3 atom%, and O atom concentration is 57. The composition of the second layer of the gas barrier layer was 1. atom%, and the atomic ratio of oxygen atoms to silicon atoms was 1.70. The gas barrier laminate of this example showed high gas barrier properties and passed the adhesion of the adhesive layer.

(Example 2)
(Formation of first layer containing zinc)
As a base material, a sputter target which is a sintered material formed of zinc sulfide and silicon dioxide with a polyethylene terephthalate film having a thickness of 50 μm (trade name: “Lumirror” (registered trademark) U48) manufactured by Toray Industries, Inc.) (Molar composition ratio = zinc sulfide / silicon dioxide = 80/20) was prepared.

Next, an argon gas is introduced into the sputter target using a CVD apparatus so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and an input power of 500 W is applied from a high frequency power source to generate an argon gas plasma, thereby sputtering. Thus, the [1-B] layer was formed to be 150 nm as the first layer containing zinc on one side of the substrate. The composition of the first layer was 86.7% by mass for ZnS and 13.3% by mass for SiO ₂ .

(Formation of second layer containing silicon)
In the same manner as in Example 1, a second layer containing silicon was formed to a thickness of 100 nm on the [1-B] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. The composition of the first layer of the gas barrier layer in the gas barrier laminate of this example has a zinc sulfide molar fraction of 0.85, and the composition of the second layer of the gas barrier layer is the number of oxygen atoms relative to silicon atoms. The ratio was 1.70. The gas barrier laminate of this example showed high gas barrier properties and passed the adhesion of the adhesive layer.

(Example 3)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
A second layer containing silicon was formed on the [1-A] layer by the CVD method in the same manner as in Example 1 except that the thickness was 50 nm.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the thickness of the second layer in the gas barrier layer was thinner than that of Example 1, but the gas barrier property was maintained and the adhesion of the adhesive layer was acceptable.

Example 4
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
A second layer containing silicon was formed on the [1-A] layer by the CVD method in the same manner as in Example 1 except that the thickness was 8 nm.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was slightly lowered because the thickness of the second layer in the gas barrier layer was thinner than in Examples 1 and 3, but the adhesion of the adhesive layer was acceptable.

(Example 5)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
A sputter target, which is a sintered material formed of silicon dioxide, was prepared.

Next, the sputtering target is sputtered and CVD equipment is used, argon gas is introduced so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and an applied power of 500 W is applied by a high frequency power source to generate argon gas plasma. Then, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by sputtering.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. The gas barrier laminate of this example exhibited high gas barrier properties and passed the adhesion of the adhesive layer even when the second layer formation method in the gas barrier layer was different from that of Example 1.

(Example 6)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
A second layer containing silicon was formed on the [1-A] layer by sputtering in the same manner as in Example 5 except that the thickness was 50 nm.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. The gas barrier laminate of the present example maintained the gas barrier property and passed the adhesion of the adhesive layer, although the thickness of the second layer in the gas barrier layer was thinner than that of Example 5.

(Example 7)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
A second layer containing silicon was formed on the [1-A] layer by sputtering in the same manner as in Example 5 except that the thickness was 15 nm.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was slightly lowered because the thickness of the second layer in the gas barrier layer was thinner than in Examples 5 and 6, but the adhesion of the adhesive layer was acceptable.

(Example 8)
(Formation of underlayer)
As a substrate, a polyethylene terephthalate film (trade name: “Lumirror” (registered trademark) U48, manufactured by Toray Industries, Inc.) having a thickness of 50 μm was prepared.
Next, as an undercoat layer-forming coating solution, 100 parts by mass of an acrylic composition (KAYANOVA (registered trademark FOP-1740, solid concentration 82% by mass) manufactured by Nippon Kayaku Co., Ltd.) and silicone oil (Toray Dow Corning) SH190) 0.2 parts by mass was added and diluted to a solid content concentration of 10% by mass with a mixed solvent of toluene and methyl ethyl ketone (MEK) mass ratio of 1: 1 to prepare an undercoat layer coating solution. .

Next, the base layer coating solution was applied onto a substrate with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), heated and dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays at 1.0 J / cm ^2. Then, an underlayer having a thickness of 1 μm was formed.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer having a thickness of 150 nm was formed as a first layer containing zinc on the base layer by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 1, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was improved as compared with Example 1 in which the underlayer was not laminated by adopting a configuration in which the underlayer was laminated between the base material and the gas barrier layer.

Example 9
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer having a thickness of 150 nm was formed as a first layer containing zinc on the base layer by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 3, a second layer containing silicon was formed to a thickness of 50 nm on the [1-A] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was improved as compared with Example 3 in which the underlayer was not laminated by adopting a configuration in which the underlayer was laminated between the base material and the gas barrier layer.

(Example 10)
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer having a thickness of 150 nm was formed as a first layer containing zinc on the base layer by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 4, a second layer containing silicon was formed to 8 nm on the [1-A] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was improved as compared with Example 4 in which the underlayer was not laminated by adopting a configuration in which the underlayer was laminated between the base material and the gas barrier layer.

(Example 11)
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer having a thickness of 150 nm was formed as a first layer containing zinc on the base layer by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 5, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by sputtering.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was improved as compared with Example 5 in which the underlayer was not laminated by adopting a configuration in which the underlayer was laminated between the base material and the gas barrier layer.

(Example 12)
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer having a thickness of 150 nm was formed as a first layer containing zinc on the base layer by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 6, a second layer containing silicon was formed to a thickness of 50 nm on the [1-A] layer by sputtering.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, the gas barrier property was improved as compared with Example 6 in which the base layer was not laminated by adopting a configuration in which the base layer was laminated between the base material and the gas barrier layer.

(Example 13)
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer having a thickness of 150 nm was formed as a first layer containing zinc on the base layer by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 7, a second layer containing silicon was formed to a thickness of 15 nm on the [1-A] layer by sputtering.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. The gas barrier laminate of this example had a configuration in which a base layer was laminated between the base material and the gas barrier layer, so that the gas barrier property was improved as compared with Example 7 in which the base layer was not laminated.

(Example 14)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 1, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
As a raw material of the adhesive layer containing an epoxy resin composition, bisphenol F type diglycidyl ether / bisphenol A type epoxy resin / phenol novolak type epoxy resin / phenol novolak / diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate ( A mixed composition having a ratio of (photoinitiator) = 73.2 / 2.8 / 11.3 / 11.3 / 1.4 [mass%] was prepared. Next, after the mixture composition is applied onto the second layer, it is cured by irradiation with ultraviolet rays at ² J / cm ² with a metal halide lamp, and then heated at 80 ° C. for 1 hour to be post-cured and does not contain an inorganic composition. An adhesive layer having a crosslinked structure and having a thickness of 100 μm was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, although the adhesion of the adhesive layer was acceptable, the adhesive layer does not contain an inorganic composition, so that the gas barrier property is higher than that of Example 1 except for the adhesive layer. inferior.

(Example 15)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 1, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by sputtering.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 14, an adhesive layer having a thickness of 100 μm and having a crosslinked structure containing no inorganic composition was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of the present example, the adhesion of the adhesive layer was acceptable, but the adhesive layer does not contain an inorganic composition. Therefore, the gas barrier property is higher than that of Example 5 except for the adhesive layer. inferior.

(Example 16)
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 1, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 14, an adhesive layer having a thickness of 100 μm and having a crosslinked structure containing no inorganic composition was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of this example, although the adhesion of the adhesive layer was acceptable, the adhesive layer does not contain an inorganic composition. Therefore, the gas barrier property is higher than that of Example 8 except for the adhesive layer. inferior.

(Example 17)
(Formation of underlayer)
In the same manner as in Example 8, a base layer having a thickness of 1 μm was formed on the substrate.

(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
In the same manner as in Example 5, a second layer containing silicon was formed to a thickness of 100 nm on the [1-A] layer by sputtering.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 14, an adhesive layer having a thickness of 100 μm and having a crosslinked structure containing no inorganic composition was formed.

(Gas barrier laminate)
As described above, the gas barrier laminate was obtained by laminating the base layer, the first layer, the second layer, and the adhesive layer. In the gas barrier laminate of the present example, the adhesion of the adhesive layer was acceptable, but the adhesive layer does not contain an inorganic composition. Therefore, the gas barrier property is higher than that of Example 11 except for the adhesive layer. inferior.

(Comparative Example 1)
(Formation of first layer containing zinc)
In this comparative example, it was not formed.

(Formation of second layer containing silicon)
As a substrate, a polyethylene terephthalate film (trade name: “Lumirror” (registered trademark) U48, manufactured by Toray Industries, Inc.) having a thickness of 50 μm was prepared. In the same manner as in Example 1, a second layer containing silicon was formed to a thickness of 100 nm on the base material layer by the CVD method.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Laminate)
As described above, the first layer containing zinc was not laminated, but the second layer containing silicon directly laminated on the substrate and the adhesive layer were laminated to obtain a laminate. Since the laminated body of this comparative example did not laminate | stack the 1st layer containing zinc, gas barrier property was not acquired.

(Comparative Example 2)
(Formation of first layer containing zinc)
In the same manner as in Example 1, a [1-A] layer was formed to have a thickness of 150 nm as a first layer containing zinc on one side of the substrate by sputtering.

(Formation of second layer containing silicon)
In this comparative example, it was not formed.

(Formation of adhesive layer containing epoxy resin composition)
In the same manner as in Example 1, an adhesive layer having a thickness of 100 μm including a flat inorganic composition and having a crosslinked structure was formed.

(Gas barrier laminate)
As described above, the first layer containing zinc was laminated, but the second layer containing silicon was not laminated, and an adhesive layer was laminated directly on the first layer to obtain a laminate. Since the laminated body of this comparative example did not laminate | stack the 2nd layer containing silicon, the adhesiveness of the contact bonding layer became disqualified.

(Application example)
The gas barrier laminate of the present invention can be used for solar cells and display-related electronic devices.

  As a solar cell, it can be preferably used as a sealing member for silicon solar cells, compound solar cells, organic solar cells, etc., and the gas barrier laminate of the present invention is excellent in gas barrier properties and adhesiveness. By adhering to the PET resin film or fluororesin film that constitutes the back sheet of the battery, the barrier property of the back sheet against water vapor can be greatly improved, and the durability of the back sheet and further the solar cell can be greatly improved. be able to.

  Moreover, it can use preferably as sealing members, such as a touch panel, electronic paper, a liquid crystal display, an organic electroluminescent display, and organic electroluminescent illumination, as a display body related electronic device.

  When used for a touch panel, the gas barrier property of the transparent conductive film can be improved by attaching the gas barrier laminate of the present invention to a transparent conductive film laminated with ITO or the like. Deterioration can be prevented.

  When used as a sealing member for electronic paper, liquid crystal display, organic EL display, organic EL lighting, etc., for example, flexible electronic paper using a film substrate, liquid crystal display, organic EL display, organic EL lighting, etc. By adhering the gas barrier laminate of the present invention to the transparent conductive film, diffusion film, polarizing plate, etc. constituting the product, or by sealing any part of the organic EL element or sealing the entire surface, High gas barrier property can be developed while maintaining the properties, and further flexibility can be developed. Therefore, durability improvement and long life of flexible electronic paper, liquid crystal display, organic EL display, organic EL lighting, etc. Can be achieved.

  Since the gas barrier laminate of the present invention has high gas barrier properties and adhesion to the adhesive layer, for example, food and pharmaceutical packaging applications, solar cells, touch panels, electronic paper, liquid crystal displays, organic EL displays, Although it can use suitably for display bodies, such as organic electroluminescent illumination, a use is not limited to these.

1: Base material 2: First layer 3: Second layer 4: Adhesive layer 5: Underlayer

Claims (10)

The substrate has a gas barrier layer on at least one surface, and the gas barrier layer has a first layer containing at least zinc and a second layer containing silicon in this order from the substrate, and an epoxy is formed on the second layer of the gas barrier layer. A gas barrier laminate obtained by laminating an adhesive layer containing a resin-based resin composition. The gas barrier laminate according to claim 1, further comprising an inorganic composition containing at least one inorganic component in the adhesive layer. The gas barrier laminate according to claim 1 or 2, wherein the first layer of the gas barrier layer is one of the following 1-A layer and 1-B layer.
1-A layer: a layer comprising a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide 1-B layer: a layer comprising a coexisting phase of zinc sulfide and silicon dioxide The first layer of the gas barrier layer is a 1-A layer, the zinc (Zn) atom concentration measured by ICP emission spectroscopy is 20.0 to 40.0 atom%, and the silicon (Si) atom concentration is 5. It is composed of a composition having 0 to 20.0 atom%, an aluminum (Al) atom concentration of 0.5 to 5.0 atom%, and an oxygen (O) atom concentration of 35.0 to 70.0 atom%. The gas barrier laminate according to any one of claims 1 to 3, wherein The first layer of the gas barrier layer is a 1-B layer, and the gas barrier layer has a composition in which the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier laminate according to any one of claims 1 to 4, wherein The gas barrier laminate according to any one of claims 1 to 5, wherein the gas barrier laminate has a configuration in which an underlayer is laminated between a base material and a gas barrier layer. The solar cell which uses the gas barrier laminated body in any one of Claims 1-6. The solar cell according to claim 7, wherein the solar cell is any one of a silicon solar cell, a compound solar cell, and an organic solar cell. The display body which uses the gas barrier laminated body in any one of Claims 1-6. A display device that is any one of a touch panel, electronic paper, a liquid crystal display, an organic EL display, and organic EL illumination using the display body according to claim 9.

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