JP5516029B2 - Gas barrier laminate - Google Patents

Description

  The present invention relates to a gas barrier laminate used as a packaging material for foods and drinks, pharmaceuticals, electronic components and the like, and a gas barrier laminate used for suppressing deterioration of a display element sensitive to oxygen and water vapor, such as a display. About the body.

  The main application of the gas barrier laminate of the present invention is a sealing member, particularly a sealing member for a display element such as an organic electroluminescence (organic EL) display or electronic paper for a display, Film barrier for lighting, film substrate for solar cell, film substrate for circuit board, electronic paper, supporting substrate such as electrophoretic ink or organic semiconductor, and packaging material for food and drink, pharmaceuticals and electronic parts, etc. There is no particular limitation as long as it is used.

In recent years, in the packaging field, as a packaging material for foods and drinks, pharmaceuticals, electronic components, etc., in the preservation of contents, maintenance of packaging form, quality assurance, etc., and in the display field, deterioration of display elements that are sensitive to oxygen and water vapor. In order to suppress this, a gas barrier laminate that prevents permeation of oxygen and water vapor is used.
These gas barrier laminates usually have a structure in which a base material layer, a gas barrier property-imparting layer, and the like are laminated for the purpose of preventing intrusion of oxygen and water vapor from the surface without using an adhesive. Some are obtained by laminating only by vapor deposition or coextrusion (Patent Documents 1 and 2), and others are obtained by laminating by using an adhesive (Patent Document 3).

  A laminate used as a packaging material for electronic members or a sealing member for display elements is required to have extremely high gas barrier properties. To satisfy this requirement, two or more gas barrier films are used with an adhesive. It is possible to use a laminated body that is bonded and has an improved gas barrier property. Such a gas barrier laminate can suitably prevent permeation of oxygen and water vapor from the surface.

  However, it has been found that oxygen and water vapor enter also from the end face, that is, the side face of the gas barrier laminate, and particularly from the adhesive layer that bonds the films to each other, thereby promoting the deterioration of the contents.

Japanese Patent Laid-Open No. 2003-340956 JP 2007-130857 A JP 2005-161691 A

  Therefore, the present invention can prevent the intrusion of oxygen and water vapor not only from the surface but also from the end face, and has a gas barrier laminate having transparency that can be applied to various packaging applications and display fields. The purpose is to provide.

As a result of various studies, the present inventors have found that the first transparent gas barrier film, the adhesive resin layer laminated on the first transparent gas barrier film, and the first laminated on the adhesive resin layer. 2
A transparent gas barrier film, wherein the adhesive resin layer is made of a fluorine-containing resin formed by a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group. It has been found that a laminated body characterized in that the above-mentioned object is achieved.

The present invention is characterized by the following points.
1. A laminate having a first transparent gas barrier film, an adhesive resin layer laminated on the first transparent gas barrier film, and a second transparent gas barrier film laminated on the adhesive resin layer The adhesive resin layer is a layer made of a fluorine-based resin formed by a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group. body.
2. 2. The laminate according to 1 above, wherein the fluorine-containing copolymer contains at least a fluoroolefin monomer and a hydroxyl group-containing monomer as monomer components.
3. 3. The laminate according to 1 or 2 above, wherein the curing agent is an organic polyisocyanate compound.
4). 4. The laminate according to any one of 1 to 3, wherein the adhesive resin layer further contains a silane coupling agent.
5. At least one of the first transparent gas barrier film and the second transparent gas barrier film is a vapor deposition film having a base material layer and an inorganic oxide vapor deposition layer deposited on the base material layer. The laminated body in any one of said 1-4 characterized by the above-mentioned.
6). The vapor deposition film further has a gas barrier coating film provided on the inorganic oxide vapor deposition layer, and the gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. And a film made of a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. 6. The laminate according to 5 above, wherein there is a laminate.
7). The layered product according to any one of the above items 1 to 6, wherein the adhesive resin layer has a thickness of 2 to 6 µm.
8). In the measuring method prescribed | regulated to this invention, the water vapor transmission rate from an end surface is 30 g / m < ² > * day or less, The laminated body in any one of said 1-7.

  According to the present invention, two transparent gas barrier films are bonded not only from the surface, but also by using a fluorine-based resin having a high barrier property against oxygen and water vapor and having excellent heat resistance and adhesiveness. In addition, it is possible to prevent gas and water vapor from entering from the end face and to obtain a gas barrier laminate having transparency. Hereinafter, in the present invention, the ability to prevent the entry of oxygen and water vapor from the surface is called surface gas barrier property, and the ability to prevent the entry of oxygen and water vapor from the end face is called end face gas barrier property.

  In the present invention, the adhesive resin layer made of a fluorine-based resin not only prevents the penetration of oxygen and water vapor into the layer, but also allows oxygen and water vapor to enter the interface between the layer and the transparent gas barrier film. Can be prevented. Therefore, by sealing display elements such as organic EL and electronic paper in the packaging bag made of the laminate of the present invention, deterioration of these electronic members due to exposure to oxygen or water vapor can be significantly prevented.

  Moreover, when a vapor deposition film having a base material layer and an inorganic oxide vapor deposition layer deposited on the base material layer is used as the transparent gas barrier film, the base material layer, the vapor deposition layer, and the vapor deposition layer are bonded. An interface suitable for the purpose of the present invention is formed between the conductive resin layer.

Furthermore, the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ ,
R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M). A gas barrier coating film comprising a gas barrier composition obtained by polycondensation by a sol-gel method, which contains at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. By providing this, the end face gas barrier property and the surface gas barrier property can be further improved.

It is a schematic sectional drawing which shows an example about the layer structure of the laminated body concerning this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body concerning this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body concerning this invention.

The above-described present invention will be described in more detail below.
<1> Layer Configuration of Laminate of the Present Invention As a laminate according to the present invention, for example, as shown in FIG. 1, it comprises a first and second transparent gas barrier film 1 and an adhesive resin layer 2. The laminated body which has this as a basic structure can be mentioned.
Moreover, as an example of the laminated body concerning this invention, as shown in FIG. 2, the 1st and 2nd transparent gas barrier film is a vapor deposition film which consists of the base material layer 3 and the inorganic oxide vapor deposition layer 4, respectively. A laminated body is mentioned.
As another example, as shown in FIG. 3, the first and second transparent gas barrier films are vapor deposition films each including a base layer 3, an inorganic oxide vapor deposition layer 4, and a gas barrier coating film 5. A laminated body is mentioned.

<2> Adhesive resin layer The adhesive resin layer constituting the laminate according to the present invention is a fluorine-based copolymer formed by a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group. Made of resin. The adhesive resin layer bonds the first transparent gas barrier film and the second transparent gas barrier film with an excellent adhesive force, and further prevents the permeation of oxygen and water vapor from the end surface into the laminate. Fulfill.

Fluorine-containing copolymer The fluorine-containing copolymer used in the present invention is a polymer soluble in a general-purpose organic solvent, and can be copolymerized with the fluoroolefin monomer (A) and the fluoroolefin monomer. The crosslinkable group-containing monomer (B) is used as a monomer component.
Examples of the fluoroolefin monomer (A) include tetrafluoroethylene, trifluoroethylene, hexafluoropropylene and the like. Since high adhesive strength can be obtained, trifluoroethylene represented by Formula 1: CF ₂ = CFX (where X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group) is preferable. More preferably, it is chlorotrifluoroethylene in which X in the formula is a chlorine atom.

As the crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer, a monomer having a hydroxyl group, an epoxy group, a carboxyl group, an amide group, an amino group or a hydrolyzable silyl group as the crosslinkable group. The body is mentioned. Specifically, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether , Hydroxyl group-containing monomers such as 2-hydroxyethyl allyl ether and 4-hydroxybutyl allyl ether, epoxy group-containing monomers such as glycidyl vinyl ether and glycidyl (meth) acrylate, carboxyl groups such as acrylic acid and methacrylic acid Monomers, amide group-containing monomers such as (meth) acrylamide and N-methylolacrylamide, and amino groups such as aminoalkyl vinyl ether and aminoalkyl allyl ether Hydrolyzable silyl group-containing monomers such as monomers, trimethoxyvinylsilane, triethoxyvinylsilane, γ-methacryloxypropyltrimethoxysilane, etc. can be mentioned, but they can be easily processed by the gravure coating method and can be cured appropriately. Since the speed is obtained, a hydroxyl group-containing monomer, in particular, formula 2: CH ₂ = CHR ¹ [wherein R ¹ is —OR ² to —CH ₂ OR ² (where R ² is an alkyl group having a hydroxyl group) It is particularly preferable to use a hydroxyl group-containing monomer represented by

In addition to the fluoroolefin monomer and the crosslinkable group-containing monomer, the fluorine-containing copolymer used in the present invention further improves coating properties and coating properties (hardness, flexibility, etc.) as necessary. Therefore, a monomer copolymerizable with the above two types of monomers can be copolymerized and contained. As such a monomer, β-methyl-substituted α-olefin monomer represented by the formula 3: CH ₂ = CR (CH ₃ ) [wherein R is an alkyl group having 1 to 8 carbon atoms] Compound (C), Formula 4: CHR ³ = CHOR ³ (CH ₃ ), wherein R ³ is an alkyl group having 1 to 8 carbon atoms, Formula 5: A vinyl ether monomer (E) represented by CH ₂ ═CHR ³ , wherein R ³ is —OR ⁴ to —CH ₂ OR ⁴ (where R ⁴ is an alkyl group having a carboxyl group), and And other monomer (F) which does not have a crosslinkable functional group and can be copolymerized with the monomers of the above formulas 1 to 5.

  In the present invention, a copolymer containing all of the monomers (A) to (F) is particularly preferable because the coating property is stabilized.

  The fluorine-containing copolymer used in the present invention contains a fluoroolefin monomer (A) and a crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer as essential components. Accordingly, at least one monomer selected from the monomers (C), (D), (E), and (F) is added, and a known method such as emulsion polymerization, solution polymerization, or suspension polymerization is performed. It can be obtained by copolymerization.

  The number average molecular weight of the fluorine-containing copolymer of the present invention is 1,000 to 500,000, preferably 3000 to 100,000 as a value in terms of polystyrene measured by gel permeation chromatography (GPC). When the number average molecular weight is less than 1000, the barrier property against water vapor and oxygen may be lowered. Moreover, when larger than 500,000, it may be inferior to coating property.

  The composition ratio between the fluoroolefin monomer (A) in the fluorine-containing copolymer of the present invention and the crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer is in terms of mole. , (A) :( B) is preferably 1: 1 to 10: 1, particularly preferably 2: 1 to 5: 1. If the ratio of the monomer (A) is too low, the barrier property against water vapor and oxygen may be lowered, and if it is too high, the coatability may be inferior.

  The total amount of the monomers (C), (D), (E), and (F) is not particularly limited as long as the effects of the present invention are not impaired. It is preferable that it is 5-30 mol% with respect to quantity, and it is further more preferable that it is 10-25 mol%. The composition ratio between the monomers (C), (D), (E) and (F) can be appropriately set according to the application.

  A compounding agent known to those skilled in the art may be added to the fluorine-containing copolymer used in the present invention, if necessary.

Curing Agent As the curing agent used in the present invention, a compound that reacts with the above-described crosslinkable group to form a crosslink can be used. The curing agent for the hydroxyl group-containing monomer is a compound having an isocyanate group or a carboxyl group, and an organic polyisocyanate compound having an isocyanate group is preferable because a suitable curing reaction rate can be obtained. Examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate. , N-pentane-1,4-diisocyanate, and trimers thereof, adducts and burettes thereof, or polymers having two or more isocyanate groups, and further blocked. Examples include isocyanates. Preferably, it is a trimer of isophorone diisocyanate or hexamethylene diisocyanate. This is because the compatibility with the fluorine-containing copolymer is good, the curing rate is appropriate, and the laminate strength is high. Moreover, the compound which has a hydroxyl group, a carboxyl group, an amide group, an amino group, or an isocyanate group can be used for the hardening | curing agent with respect to an epoxy group containing monomer. Moreover, the compound which has a hydroxyl group, an amino group, an isocyanate group, or an epoxy group can be used for the hardening | curing agent with respect to a carboxyl group-containing monomer. Moreover, the compound which has an epoxy group can be used for the hardening | curing agent with respect to an amide group containing monomer. Moreover, the compound which has a carboxyl group, an epoxy group, or an isocyanate group can be used for the hardening | curing agent with respect to an amino group containing monomer. Moreover, the compound which has an amino group or an isocyanate group can be used for the hardening | curing agent with respect to a hydrolysable silyl group containing monomer.

  Examples of the compound having a hydroxyl group include 1,4-bis-2'-hydroxyethoxybenzene and bishydroxyethyl terephthalate. Examples of the compound having a carboxyl group include aliphatic dibasic acids such as fumaric acid, succinic acid, adipic acid, and azelaic acid, and acid anhydrides such as phthalic anhydride. Examples of the compound having an epoxy group include terephthalic acid diglycidyl ester and p-hydroxybenzoic acid diglycidyl ester.

Silane Coupling Agent In the present invention, the adhesive resin layer may contain a silane coupling agent in addition to the fluororesin, in order to further increase the adhesive strength and the barrier property against oxygen and water vapor.
As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used.
In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like can be used. These silane coupling agents may be used alone or in combination of two or more.
As a compounding quantity of a silane coupling agent, it can set suitably in the range by which the effect of this invention is not impaired, For example, it is preferable in it being 0.05-10 mass% with respect to a fluorine resin, More preferably, it is 0.1-5 mass%. If the amount is less than 0.05% by mass, a sufficient effect cannot be obtained. If the amount is more than 10% by mass, the reaction rate may be slow, which may not be preferable.

Method for Preparing Adhesive Resin Layer A method for preparing the adhesive resin layer used in the present invention will be described using a fluorine-containing copolymer containing a hydroxyl group as an example. The fluorine-containing copolymer containing a hydroxyl group and the curing agent are dissolved in a solvent in which one or two or more of acetates, ketones, ethers, aromatic hydrocarbons and the like are mixed. Here, the curing agent is a group that reacts with the crosslinkable group in the curing agent, such as an isocyanate group or a carboxyl group, with respect to 1 equivalent of the crosslinkable group in the fluorine-containing copolymer, such as a hydroxyl group (—OH group). Is added in an amount of 0.1 to 5.0 equivalents, preferably 0.5 to 1.5 equivalents. Coating and drying the solution containing the fluorine-containing copolymer and the curing agent on the first transparent gas barrier film using a known coating method such as roll coating, gravure coating, or bar coating. Thus, an adhesive resin layer is formed. The layer thickness of the adhesive resin layer is 2 to 6 μm, more preferably 3 to 5 μm. In order to ensure the laminate strength, 2 μm or more is necessary, but in order to minimize the moisture permeation from the end face, the thickness of the adhesive resin layer should be as thin as possible, and the layer thickness should be 6 μm. If it exceeds, the end face gas barrier property required as a sealing member such as a display element may not be maintained.

<3> Transparent gas barrier film As the transparent gas barrier film constituting the laminate of the present invention, various transparent gas barrier films can be used depending on the application, but they are used as sealing members for display elements. Therefore, it is preferable to use a transparent film having a water vapor permeability from the surface of 0.1 g / m ² · day or less. In the present invention, the water vapor permeability from the surface is determined by ASTM.
According to F1249-90, it is a value measured using AQUATRAN manufactured by MOCON in an environment of 60 ° C. and 90% RH. Further, in the present invention, the term “transparent” is not limited as long as it has necessary transparency depending on the application, and includes colorless or colored and transparent ones. In particular, it is used as a sealing member such as a display element of a display. In this case, high transparency is required. For example, the average light transmittance in the visible light region of 380 nm to 780 nm is 80% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

Vapor-deposited film As the transparent gas barrier film used in the present invention, for example, a vapor-deposited film having a substrate layer and an inorganic oxide vapor-deposited layer deposited on the substrate layer is particularly preferably used.
The deposited film not only exhibits excellent surface gas barrier properties and transparency, but also has high adhesion between the base material layer and the inorganic oxide deposited layer, and oxygen and water vapor are less likely to enter the interface between the layers. Therefore, it shows a good end face gas barrier property.

As the base layer of the base layer deposited film, it has excellent chemical or physical strength, can withstand the conditions for forming the inorganic oxide deposited layer, etc., and keeps it well without impairing the properties of the inorganic oxide deposited layer. Plastic films that can be obtained can be used.
Examples of such plastic films include polyolefin films such as polypropylene and polyethylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyamide films, polycarbonate films, cyclic olefin copolymer films, cyclic olefin polymer films, liquid crystal polymer films, Polyimide film, TAC film, and other various resin films or sheets can be used.
In particular, when used as a sealing member such as a display element of a display, it is preferable to use a film made of a cyclic olefin copolymer, among the films made of the above plastic material, from the viewpoint of transparency and heat resistance.
The layer thickness of the base material layer of this invention is 12-400 micrometers, More preferably, it is 50-200 micrometers.
The plastic film may be subjected to, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, or other pretreatment. Can be applied arbitrarily. The surface pretreatment is carried out as a method for improving the adhesion between the plastic film and the inorganic oxide vapor deposition layer. As a method for improving the adhesion, for example, the surface of the plastic film is used. In addition, a primer coating agent layer, an undercoat layer, a vapor deposition anchor coating agent layer, or the like can be arbitrarily formed in advance.

Inorganic Oxide Deposition Layer An inorganic oxide deposition layer suitable for the present invention is described below from the viewpoints of tight adhesion to the substrate layer and the adhesive resin layer, transparency, and surface and end face gas barrier properties. A vapor deposition layer made of an inorganic oxide can be applied.
The material for forming the inorganic oxide vapor deposition layer may be any material having transparency and gas barrier properties such as oxygen and water vapor. For example, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide In addition, oxides such as titanium oxide, boron oxide, hafnium oxide, and barium oxide are preferable, and aluminum oxide, silicon oxide, silicon oxynitride, and silicon oxide carbide are particularly preferable in terms of gas barrier properties and production efficiency. .
As a method for forming the inorganic oxide vapor deposition layer, vacuum deposition, reactive vapor deposition, ion beam assisted vapor deposition, sputtering, ion plating, plasma CVD, thermal CVD, and other vacuum film formation methods can be used. Can be mentioned.

Moreover, the inorganic oxide vapor deposition layer may consist of a single layer formed by a single vapor deposition step, or may have a multilayer structure formed by repeating the vapor deposition step a plurality of times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same forming method or by different forming methods. Good. For example, a vapor deposition film made of silicon oxide may be formed on the base material layer by chemical vapor deposition, and then a vapor deposition film made of aluminum oxide may be formed by physical vapor deposition.
The layer thickness of the inorganic oxide vapor deposition layer can be appropriately set within the range of 5 to 100 nm, more preferably 10 to 50 nm, as the thickness of the entire layer. If it exceeds 100 nm, the flexibility will be reduced, and the deposited layer may be cracked by external forces such as bending and pulling after film formation, transparency may be reduced, and the stress of the material itself will increase. Coloring is not preferable. On the other hand, if the thickness exceeds 100 nm, productivity is remarkably lowered, and further, protrusions tend to be formed due to abnormal grain growth, which is not preferable. On the other hand, when the thickness of the inorganic compound layer is less than 5 nm, the transparency is good, but it is difficult to obtain a uniform layer and it is difficult to sufficiently perform the gas barrier function.

Gas barrier coating film In the present invention, by further providing a gas barrier coating film as described below on the inorganic oxide vapor deposition layer, not only a more excellent surface gas barrier property can be obtained, but also the above-mentioned adhesiveness. The tight adhesion with the resin layer is enhanced, and a higher end face gas barrier property is obtained.
In the present invention, the gas barrier coating film is a film obtained by applying and drying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.
The alkoxide used in the gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal And n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M).
As the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum or the like can be used as the metal atom M. Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.
In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an alkoxysilane in which M is Si can be used. As the alkoxysilane, for example, tetramethoxy Examples thereof include silane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like.

  Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 mass parts with respect to 100 mass parts of total amounts of said alkoxide. In the above, if it exceeds 500 parts by mass, the brittleness of the formed gas barrier coating film is increased, and its weather resistance and the like are also deteriorated.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization) Degree = 1,400) and Gohsenol NH-18 (degree of saponification = 98-99%, degree of polymerization = 1700) and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used. Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition for forming a gas barrier coating film according to the present invention. Suitable silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Amino group-containing silane coupling agents such as aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2 -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Coupling agent, 3-mercaptopro Examples include mercapto group-containing silane coupling agents such as rumethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. .

  The gas barrier composition used in the present invention can be prepared by hydrolyzing and polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water and an organic solvent.

The gas barrier coating film is formed by applying the gas barrier composition on the inorganic oxide vapor-deposited layer, at a temperature of 20 ° C. to 200 ° C., preferably 140 ° C. or higher, and below the melting point of the plastic film constituting the base material layer. It can be formed by heat treatment for 10 seconds to 10 minutes.
Moreover, as an acid used in preparation of said gas-barrier composition, organic acids, such as mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, and an acetic acid, tartaric acid, etc. can be used, for example. Furthermore, as the organic solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, or the like can be used.

Further, regarding the gas barrier composition, the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.
When the above gas barrier composition is applied on the inorganic oxide vapor deposition layer and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed and a transparent gas barrier coating film is formed. Is done.
Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the inorganic oxide deposition layer, close adhesion between the inorganic oxide deposition layer and the gas barrier coating film, etc. Will be good.

  By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good surface gas barrier properties.

  In the present invention, the inorganic oxide vapor deposition layer and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved. In addition, a better surface gas barrier property can be exhibited by a synergistic effect.

In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, a gas barrier coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed.
In the present invention, in order to obtain a higher surface gas barrier property, after providing the gas barrier coating film, the inorganic oxide vapor deposition layer and the gas barrier coating film are alternately or once in this order. A transparent gas barrier film may be formed by repeatedly laminating as described above and preferably forming the gas barrier coating film to be the outermost layer.

<4> Bonding In the present invention, on the first transparent gas barrier film, a solution containing a fluorine-containing copolymer and a curing agent is applied and dried to form an adhesive resin layer. A 2nd transparent gas barrier film is laminated | stacked on a layer, and the laminated body of this invention is obtained.
Here, when either or both of the first and second transparent gas barrier films are the above-described vapor deposition films, the gas barrier coating film is formed so that the inorganic oxide vapor deposition layer is in contact with the adhesive resin layer. In the case of being provided, it is preferable from the viewpoint of the handleability of the laminate that the gas barrier coating film is bonded so as to be in contact with the adhesive resin layer and the base material layer is the surface layer of the laminate.

The adhesive resin layer of the present invention firmly adheres to the inorganic oxide vapor deposition layer or the gas barrier coating film, and prevents the entry of oxygen and water vapor into the bonded boundary surface, thereby further improving the end face gas barrier property.
Moreover, as one aspect of the present invention, one or more additional layers, for example, a transparent gas barrier film, may be laminated on either or both of the first and second transparent gas barrier films. When laminating a film, a high end face gas barrier property can be maintained even if the thickness of the laminate is increased by laminating the film via the adhesive resin layer made of the fluororesin of the present invention. .

When many transparent gas barrier films are bonded to obtain a high surface gas barrier property, the end surface gas barrier property is generally lowered instead of improving the surface gas barrier property. However, in order to use it suitably as a sealing member for a display element, the laminate needs to exhibit both excellent surface gas barrier properties and end surface gas barrier properties. In particular, for the end face gas barrier property, the water vapor permeability from the end face is 30 g / m ² · day or less, more preferably 15 g / m ² · day, as a measured value of the water vapor permeability from the end face based on the method described below. In the following, it is required to show a low value of 10 g / m ² · day or less, but according to the present invention, this requirement can be achieved.

<5> Use of Laminate The laminate of the present invention can be used as various packaging materials or support base materials, and in particular, can be suitably used as a sealing member such as a display element in a display. it can.
As a packaging bag comprising the laminate of the present invention, a laminate for bag making obtained by laminating a heat-sealable resin film on one surface of the laminate using the laminate of the present invention is folded in two. Or two of them, and the heat-sealable resin film face to face each other, and the ends are heat-sealed to form a cylindrical packaging bag, and then the bottom is sealed A packaging bag can be manufactured by filling an object and sealing the top.

As the bag-making method, the bag-making laminate as described above is folded or overlapped so that the inner layer faces are opposed to each other, and the peripheral edge thereof is, for example, a side seal type or a two-side seal type. , Three-side seal type, four-side seal type, envelope sticker seal type, jointed seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. Various forms of packaging bags can be produced.
In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

When the laminate of the present invention is used as a sealing member for a display element or the like, the display element may be enclosed in a packaging bag composed of the laminate of the present invention, or manufactured from the laminate of the present invention. You may enclose between the laminated body for bags, and a board | substrate.
When the display element is enclosed between the bag-making laminate and the substrate, such a substrate may be soft or hard, has gas barrier properties, and has a display element installed. The heat-sealable resin film of the laminate for bag making may have a surface that can be fused.
Examples of the display element to be enclosed include an organic EL display element, an electrophoretic display element, a liquid crystal display element, a light emitting diode display element, and the like, but are not limited thereto, and are described in, for example, Special Tables 2004-526210 and the like. Things can be applied.

  Next, the present invention will be specifically described with reference to examples.

[Example 1]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, which is mounted on a winding roll of a wind-up vacuum deposition apparatus, and then conveyed at a line speed of 600 mm / min. Using a sputtering apparatus, argon gas 500 sccm is introduced, plasma treatment is performed at an output of 20 kW, a plasma treatment surface with an inert gas is formed on one surface of the base film, and then the plasma treatment surface is formed on the plasma treatment surface. A vapor deposition layer made of aluminum oxide having a thickness of 10 nm was formed under the following vapor deposition conditions by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ⁻⁴ mbar
Degree of vacuum in the take-up chamber: 2 × 10 ^-2 mbar
Electron beam power: 25kw
Film transport speed: 600 m / min
Thereafter, using another magnetron sputtering apparatus, oxygen gas 1000 sccm was introduced, plasma treatment was performed at an output of 5 kW, and the plasma treatment surface by oxygen gas was applied to the surface of the aluminum oxide vapor deposition layer. Was formed and wound up.

(2) On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A liquid mixture consisting of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.

Next, using the gas barrier composition produced above on the plasma-treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (dry operation state).

(3) Next, the base film on which the first gas barrier coating film is formed as described above is used, and this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus, and the first gas barrier coating film is formed. A plasma-treated surface with an inert gas was formed on this surface, and then a 10 nm-thick aluminum oxide vapor deposition layer was formed on the plasma-treated surface under the same conditions as in (1) above.
Thereafter, using another magnetron sputtering apparatus, oxygen gas 500 sccm was introduced, plasma treatment was performed at an output of 3 kW, and the plasma treatment surface by oxygen gas was applied to the surface of the aluminum oxide vapor deposition layer. Was formed and wound up.
(4) Using the gas barrier composition produced in (2) above on the plasma-treated surface with oxygen gas formed in (3) above, this is coated by gravure roll coating, and then at 100 ° C. Heat treatment was carried out for 30 seconds to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state), thereby producing first and second transparent gas barrier films.

(5) The first transparent gas barrier film produced in (4) above is mounted on the first delivery roll of a dry laminating machine, and a solution having the following composition is applied to the gas barrier coating film surface with a gravure roll coat It was applied using a method and dried to form an adhesive resin layer (layer thickness: 4 μm).
(composition)
・ 100 parts by mass of fluoroolefin-hydroxyl group-containing vinyl ether copolymer (solid content 60%, manufactured by Daikin Industries, Ltd., Zeffle GK550)
-Hexamethylene diisocyanate trimer 60 parts by mass (solid content 70%) (amount equivalent to 1.1 equivalent to 1 equivalent of hydroxyl group of fluoroolefin-hydroxyl group-containing vinyl ether copolymer)
-160 parts by mass of ethyl acetate-0.5 parts by mass of silane coupling agent (glycidoxypropyltrimethoxysilane) (6) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in (4) above Was laminated to face the adhesive resin layer, and the curing reaction was promoted at 80 ° C. for 72 hours to produce a laminate according to the present invention.

[Example 2]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and this is mounted on a feeding roll of a plasma chemical vapor deposition apparatus. A deposited layer of silicon oxide having a thickness of 10 nm was formed on the corona-treated surface of the film.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film ^- forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 300m / min
Power: 35kW

(2) Next, the biaxially stretched polyethylene terephthalate film on which a 10 nm-thick silicon oxide vapor deposition layer was formed as described above was used, and this was mounted on a take-up roll of a wind-up type vacuum vapor deposition apparatus. And a magnetron sputtering device is used on the surface of the 10 nm thick silicon oxide vapor-deposited layer of the biaxially stretched polyethylene terephthalate film, the line speed is 600 m / min, argon gas is introduced at 500 sccm, and the output is 20 kW. Plasma treatment is performed to form a plasma treatment surface, and then the following vacuum deposition method using an electron beam (EB) heating method is performed while supplying oxygen gas to the plasma treatment surface using aluminum as an evaporation source. An aluminum oxide vapor deposition film having a thickness of 10 nm was formed according to the vapor deposition conditions of
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ⁻⁴ mbar
Degree of vacuum in the winding chamber; 2 × 10 ⁻² mbar
Electron beam power: 25 kW
Film transport speed: 600 m / min
Next, immediately after forming the 10 nm-thick aluminum oxide vapor deposition film as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 9 kw, oxygen gas (O ₂ ): argon gas. (Ar) = 7.0: 2.5 (unit: slm) is used, oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6.0 × 10 ⁻² mbar and a processing speed of 600 m / min. A plasma-treated surface was formed in which the surface tension of the deposited surface of the aluminum oxide was improved by 54 dyne / cm or more.

(3) On the other hand, a colorless and transparent gas barrier composition was obtained in the same manner as in Example 1 (2), and this was coated on the plasma-treated surface formed in (2) above by a gravure roll coating method. Subsequently, it heat-processed for 30 second at 100 degreeC, the gas barrier coating film of thickness 0.4g / m < ² > (dry operation state) was formed, and the 1st and 2nd transparent gas barrier film was manufactured.
(4) The first transparent gas barrier film produced in the above (3) is mounted on the first delivery roll of the dry laminating machine, and the gas barrier coating film surface is applied in the same manner as in Example 1 (5). An adhesive resin layer (layer thickness: 4 μm) was formed.
(5) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (3) is dry-laminated facing the adhesive resin layer, and the curing reaction is promoted at 80 ° C. for 72 hours, The laminated body concerning this invention was manufactured.

[Example 3]
(1) In the same manner as described in (1) and (2) of Example 2, on a biaxially stretched polyethylene terephthalate film (thickness 12 μm), a silicon oxide vapor deposition layer (thickness 10 nm) and aluminum oxide The vapor deposition layer (thickness 10 nm) was provided in order, the plasma processing surface was formed in the vapor deposition layer surface of the aluminum oxide, and it was set as the 1st and 2nd transparent gas barrier film.
(2) Next, the first transparent gas barrier film produced in the above (1) is mounted on the first delivery roll of the dry laminating machine, and the plasma treatment surface thereof is the same as in Example 1 (5). An adhesive resin layer (layer thickness: 4 μm) was formed.
(3) Next, the plasma processing surface of the second transparent gas barrier film produced in the above (1) is dry laminated so as to face the adhesive resin layer, and the curing reaction is promoted at 80 ° C. for 72 hours. A laminate according to the invention was produced.

[Example 4]
(1) The first transparent gas barrier film produced in the same manner as in Example 1 (1) to (4) is mounted on the first delivery roll of a dry laminating machine, and the gas barrier coating film surface is provided with the following The solution having the composition was applied using a gravure roll coating method and dried to form an adhesive resin layer (layer thickness: 4 μm).
(composition)
・ 100 parts by mass of fluoroolefin-amide group-containing (meth) acrylamide copolymer (solid content 70%, manufactured by Asahi Glass, Lumiflon)
-Epoxy curing agent 60 parts by mass (solid content 75%, manufactured by Mitsubishi Chemical, JER, 1.1 equivalent to 1 equivalent of amide group (-NH ₂ group))
200 parts by mass of ethyl acetate 0.5 parts by mass of silane coupling agent (glycidoxypropyltrimethoxysilane) (2) Next, a second transparent gas barrier film produced in the same manner as in Example 1 (4) The gas barrier coating film surface was dry laminated so as to face the adhesive resin layer, and the curing reaction was promoted at 80 ° C. for 72 hours to produce the laminate of the present invention.

[Comparative Example 1]
Except for forming an adhesive resin layer (4 μm) using a two-component curable polyurethane adhesive (manufactured by Mitsui Chemicals, main ingredient Takelac A-515 / curing agent Takenate A-50), the same procedure as in Example 1 was performed. A laminate was produced.

[Comparative Example 2]
Except that the adhesive resin layer (4 μm) was formed by using a two-component curable polyurethane adhesive (manufactured by Mitsui Chemicals, main ingredient Takelac A-515 / curing agent Takenate A-50), the same procedure as in Example 2 was performed. A laminate was produced.

[Evaluation of gas barrier properties]
(1) Heat-pressing a heat-sealable resin film (olefin-based hot melt film: Kurashiki Spinning Co., Ltd., Clanbetter M4, thickness 30 μm) on one side of the laminates produced in Examples 1-4 and Comparative Examples 1-2 110 ° C., 5 seconds, 0.1 MPa) to produce a laminate for evaluation.
(2) A flexible printed circuit board (thickness 100 μm) with an aluminum electrode on a polyimide film, and an electronic ink sheet (thickness 100 μm) with an ITO transparent electrode on a polyethylene terephthalate film and uniformly coated with microcapsules Prepared. The electrophoretic display element was manufactured by superimposing the surface of the flexible printed board on which the aluminum electrode was applied and the surface of the electronic ink sheet on which the microcapsules were applied. In this display element, the black pigment piece (negatively charged) and the white pigment piece (positively charged) in the microcapsule move according to the voltage applied to the aluminum electrode, so that a black and white image can be formed. It is configured.
(3) The display element was inserted while the heat-sealable resin film surfaces of the evaluation laminate produced in (1) were disposed so as to face each other, and hot press (110 ° C., 5 seconds, 0.1 MPa). ) Was sealed on all sides to produce a display module for evaluation.
(4) Connect the evaluation display module to the drive device, and in the environment of 60 ° C. and 90% RH, the brightness at the time of white display and the brightness at the time of black display are measured by Topcon Technohouse Co., Ltd. color luminance meter BM-5AS. The contrast ratio (= brightness during white display / brightness during black display) was calculated.

When oxygen and water vapor enter the inside from the surface and end face of the laminate, the movement of the white pigment and the black pigment in the microcapsule is hindered, and the contrast ratio is lowered.
The results are shown in Table 2.

[Measurement method of water vapor permeability from end face]
(1) A heat-sealable resin film (olefin-based hot melt film: Kurashiki Spinning Co., Ltd., Clanbetter M4, thickness 30 μm) is adhered to one side of the laminate by a hot press (110 ° C., 5 seconds, 0.1 MPa). The laminate for evaluation is manufactured.
(2) After preparing two laminates for evaluation produced in the above (1), superimposing them so that the heat-sealable resin film faces each other, heat-sealing three sides, and adding 10 g of calcium chloride The remaining one side is heat-sealed to produce an evaluation bag having an inner dimension of 100 mm × 100 mm and a seal width of 3 mm.
(3) The evaluation bag produced above is allowed to stand in an environment of 60 ° C. and 90% RH, and the weight increase of calcium chloride after 24 hours is measured.
(4) On the other hand, in accordance with ASTM F1249-90, using an AQUATRAN manufactured by MOCON in an environment of 60 ° C. and 90% RH, the laminate for evaluation is 0.01 m ² per 24 hours as follows. Measure the amount of water vapor permeation in the surface direction.
(5) Subtract twice the measured value of (4) (water vapor transmission amount in the surface direction per 0.01 m ² ) from the measured value of (3) above (water vapor transmission amount of the evaluation bag). The obtained value is divided by the area of the end face of the evaluation bag, and the value obtained thereby is taken as the water vapor permeability from the end face of the laminate.
Water vapor transmission rate from end face = {(water vapor transmission rate of evaluation bag) −2 × (water vapor transmission rate in surface direction per 0.01 m ² )} / (area of end surface of evaluation bag)

[Evaluation of end face gas barrier properties]
Based on the above method, the water vapor permeability from the end face was measured for each of the laminates produced in Examples 1-4 and Comparative Examples 1-2.
The results are shown in Table 3.

[Evaluation results]
The display modules for evaluation using the laminates of Examples 1 to 4 had a contrast ratio of 30 or more even after 200 hours, and almost no deterioration was observed. On the other hand, in the display modules for evaluation using the laminates of Comparative Examples 1 and 2, the contrast ratio was significantly reduced after 200 hours.
Moreover, although the laminated body of Examples 1-4 and Comparative Examples 1-2 showed the substantially equal value about the water vapor transmission amount of the surface direction, the water vapor transmission amount of the bag for evaluation was the same as that of Examples 1-4. The laminated body showed a smaller value than the laminated bodies of Comparative Examples 1 and 2. In the laminates of Examples 1 to 4, the adhesive resin layer made of a fluorine-based resin prevents the permeation of water vapor from the end surface, so that the water vapor permeability from the end surface is suppressed to an extremely low value.

1. 1. Transparent gas barrier film 2. Adhesive resin layer Base material layer 4. 4. Inorganic oxide vapor deposition layer Gas barrier coating film

Claims (5)

A laminate having a first transparent gas barrier film, an adhesive resin layer laminated on the first transparent gas barrier film, and a second transparent gas barrier film laminated on the adhesive resin layer a is, adhesive resin layer, Ri layer der consisting formed fluororesin by a curing agent that reacts with the fluorine-containing copolymer and the crosslinking group having a crosslinkable group, the crosslinkable group The fluorine-containing copolymer having at least a fluoroolefin monomer and a hydroxyl group-containing monomer as monomer components, and the thickness of the adhesive resin layer is 2 to 6 μm Laminated body. The laminate according to claim 1 , wherein the curing agent is an organic polyisocyanate compound. The laminate according to claim 1 or 2 , wherein the adhesive resin layer further contains a silane coupling agent. At least one of the first transparent gas barrier film and the second transparent gas barrier film is a vapor deposition film having a base material layer and an inorganic oxide vapor deposition layer deposited on the base material layer. The laminate according to any one of claims 1 to 3 , wherein the laminate is characterized in that The vapor deposition film further has a gas barrier coating film provided on the inorganic oxide vapor deposition layer, and the gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. And a film made of a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. The laminate according to claim 4, wherein there is a laminate.

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