JPWO2018047422A1 - Gas barrier laminate and sealing body - Google Patents

Abstract

Provided is a gas barrier laminate having a configuration in which a gas barrier layer containing a polymer compound and subjected to a modification treatment and an adhesive layer are directly laminated. The adhesive composition which is a material for forming the adhesive layer of the gas barrier laminate of the present invention contains at least a polyfunctional epoxy compound (B) and further contains a polyolefin resin (A), or The water vapor transmission rate of a predetermined sheet-like material formed from the adhesive composition is adjusted to be 200 g / m 2 / day or less. Thus, the gas barrier laminate of the present invention is highly effective in suppressing the penetration of water into the object to be sealed via the adhesive layer, and has excellent interlayer adhesion, so that the deterioration of the object to be sealed is suppressed. It can be a highly effective sealant.

Description

  BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a gas barrier laminate and a sealed body in which an object to be sealed is sealed with the gas barrier laminate.

In recent years, a gas barrier film having gas barrier properties in place of a glass plate as a substrate having electrodes in order to realize reduction in thickness, weight and flexibility of displays such as liquid crystal displays and electroluminescence (EL) displays. Is used.
Moreover, the film which has a new function is also developed by laminating | stacking another layer on a gas barrier film.
For example, Patent Document 1 describes a pressure-sensitive adhesive sheet formed by forming a pressure-sensitive adhesive layer on a gas barrier layer of a substrate with a gas barrier layer (gas barrier film). Patent Document 1 describes that by using the pressure-sensitive adhesive sheet, an organic EL element or the like can be efficiently sealed.

WO 2012/032907

  Generally, when a resin layer containing a resin is directly laminated on the gas barrier layer of a gas barrier film, the affinity between the gas barrier layer and the resin is low, so the interlayer between the gas barrier layer and the resin layer Problems with adhesion may occur. In particular, when a gas barrier layer containing a polymer compound and subjected to a modification treatment is used, the interlayer adhesion between the gas barrier layer and the resin layer is often poor.

On the other hand, in Patent Document 1, no study is made on the interlayer adhesion between the gas barrier layer and the pressure-sensitive adhesive layer. In the case of sealing an organic EL element using a pressure-sensitive adhesive sheet as described in Patent Document 1, when the interlayer adhesion between the gas barrier layer and the pressure-sensitive adhesive layer is low, moisture or the like infiltrates from between the two layers. The deterioration of the light emission characteristics of the organic EL element tends to occur.
In addition, the sealing material used to seal the organic EL element is required to have the property of suppressing the penetration of water not only to the gas barrier layer but also to the adhesive layer (pressure-sensitive adhesive layer). .

  The present invention has been made in view of the above situation, and has a high effect of suppressing the penetration of water into an object to be sealed via an adhesive layer, and a gas barrier laminate having excellent interlayer adhesion, An object of the present invention is to provide a sealed body obtained by sealing an object to be sealed with the gas barrier laminate.

  The present inventors contain at least a polyfunctional epoxy compound in an adhesive composition which is a forming material of an adhesive layer containing a polymer compound and directly laminated with a gas barrier layer subjected to a modification treatment, The above problems can be solved by further containing a specific resin in the adhesive composition, or by adjusting the water vapor transmission rate of a predetermined sheet-like material formed from the adhesive composition to be a predetermined value or less. It has been found that it can be solved and the present invention has been completed.

That is, the present invention relates to the following [1] to [11].
[1] A gas barrier layer containing a polymer compound and subjected to a modification treatment,
An adhesive layer formed from an adhesive composition containing a polyolefin resin (A) and a polyfunctional epoxy compound (B),
A gas barrier laminate having a configuration in which the gas barrier layer and the adhesive layer are directly laminated.
[2] The gas barrier laminate according to the above [1], wherein the component (A) contains a modified polyolefin resin (A1).
[3] The gas barrier laminate according to the above [2], wherein the component (A1) is an acid-modified polyolefin resin.
[4] The gas barrier laminate according to any one of the above [1] to [3], wherein the storage elastic modulus G ′ at 80 ° C. of the adhesive layer is 0.3 MPa or less.
[5] The content according to any one of the above [1] to [4], wherein the content of the component (A) is 5 to 90% by mass with respect to the total amount of the active components of the adhesive composition. Gas barrier laminate.
[6] Any one of the above [1] to [5], wherein the content of the component (B) is 5 to 200 parts by mass with respect to 100 parts by mass of the component (A) contained in the adhesive composition The gas barrier laminate according to one item.
[7] The gas barrier laminate according to any one of the above [1] to [6], wherein the adhesive composition further contains a tackifier (C).
[8] The gas barrier laminate according to any one of the above [1] to [7], wherein the adhesive composition further contains an imidazole curing catalyst (D).
[9] The gas barrier laminate according to any one of the above [1] to [8], wherein the adhesive composition further contains a silane coupling agent (E).
[10] A gas barrier layer containing a polymer compound and subjected to a modification treatment,
Having an adhesive layer formed of an adhesive composition containing the polyfunctional epoxy compound (B) and satisfying the following requirement (I),
A gas barrier laminate having a configuration in which the gas barrier layer and the adhesive layer are directly laminated.
Requirement (I): The water vapor transmission rate of the 50 μm-thick sheet material formed from the adhesive composition is 200 g / m ² / day or less.
[12] A seal formed by sealing an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element with the gas barrier laminate according to any one of the above [1] to [10] Stop.

  The gas barrier laminate of the present invention is highly effective in suppressing the penetration of water into the object via the adhesive layer and has excellent interlayer adhesion, so the effect of suppressing the deterioration of the object is high. It can be a sealing material.

  In the present specification, the lower limit value and the upper limit value described stepwise with respect to a preferable numerical range (for example, range such as content) can be combined independently. For example, based on the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to “10 to 60”. It can also be done.

[Configuration of gas barrier laminate]
The gas barrier laminate of the present invention comprises a gas barrier layer containing a polymer compound and subjected to a modification treatment, and an adhesive layer formed from an adhesive composition, wherein the gas barrier layer and the adhesive layer And have a configuration in which they are directly stacked.
In the gas barrier laminate (1) according to the first embodiment of the present invention (hereinafter also referred to as "the gas barrier laminate (1) according to the present invention)", the adhesive layer is formed of a polyolefin resin (A) and It is formed from the adhesive composition containing a polyfunctional epoxy compound (B).
In the gas barrier laminate (2) according to the second embodiment of the present invention (hereinafter also referred to as "the gas barrier laminate (2) according to the present invention)", the adhesive layer is formed of a polyfunctional epoxy compound (B). And formed from an adhesive composition satisfying the following requirement (I).
Requirement (I): The water vapor transmission rate of the 50 μm-thick sheet material formed from the adhesive composition is 200 g / m ² / day or less.
In the present specification, "the gas barrier laminate (1) of the present invention" and "the gas barrier laminate (2) of the present invention" are collectively referred to as "the gas barrier laminate of the present invention".

The gas barrier laminate of the present invention may have a layer other than the gas barrier layer and the adhesive layer, and may have, for example, a base layer or a release film, and has, for example, the following layer configuration Aspects can be mentioned.
-(I) Laminated body formed by laminating | stacking a base material layer / gas barrier layer / adhesive bond layer / peeling film in this order.
-(Ii) A laminate obtained by laminating a release film / gas barrier layer / adhesive layer / release film in this order.

In the embodiment of the above (i), in order to improve the adhesion between the substrate layer and the gas barrier layer, as in the embodiment of the following (iii), a primer layer is provided between the substrate layer and the gas barrier layer It is also good.
(Iii) A laminate obtained by laminating a base material layer / primer layer / gas barrier layer / adhesive layer / release film in this order.

In the aspect of said (ii), although two peeling films may be the same or may mutually differ, it is preferable that it has mutually different peeling force.
In addition, the aspect of said (i)-(iii) represents the state before use of a gas-barrier laminated body, When using, a peeling film is peel-removed normally.

Here, since the adhesive layer of the gas barrier laminate (1) of the present invention further contains a polyolefin resin (A) together with the polyfunctional epoxy compound (B), the water vapor transmission rate of the adhesive layer is It can be adjusted to be low, and it is possible to suppress the entry of moisture into the sealed object via the adhesive.
The gas barrier laminate (1) of the present invention has a gas barrier layer containing a polymer compound and subjected to a modification treatment, but an adhesive layer formed only of a polyolefin resin (A) The inventors of the present invention have found that the interlayer adhesion with the gas barrier layer is poor.
Therefore, as a result of intensive investigations by the present inventors, it is possible to obtain a polymer compound by forming an adhesive layer formed of an adhesive composition containing a polyfunctional epoxy compound (B) together with a polyolefin resin (A). It has been found that it is possible to improve the interlayer adhesion to the gas barrier layer which has been subjected to the modification treatment.
The gas barrier laminate of the present invention is made based on the findings, has a low water vapor transmission rate, can suppress the penetration of water into an object to be sealed via an adhesive, and is an excellent interlayer Since it has adhesiveness, it can become a sealing material with the high inhibitory effect of deterioration of a to-be-sealed thing.

On the other hand, in the gas barrier laminate (2) of the present invention, the types and contents of the components of the adhesive composition which is the material for forming the adhesive layer are appropriately adjusted, and the thickness of 50 μm specified in the above requirement (I) It is prepared so that the water vapor transmission rate of the sheet-like material is 200 g / m ² / day or less.
In addition, if the adhesive composition which is a formation material of the adhesive bond layer which a gas-barrier laminated body (2) has contains a polyfunctional epoxy compound (B) at least, and satisfy | fills said requirements (I), it will be polyolefin. It may contain a resin component other than the resin (A).

In the gas barrier laminate (2) of the present invention, the water vapor transmission rate of the 50 μm-thick sheet material specified in the above requirement (I) is 200 g / m ² / day or less, preferably 150 g / m ^2. / Day or less, more preferably 100 g / m ² / day or less.
When the water vapor transmission rate of the sheet-like material is 200 g / m ² / day or less, entry of moisture into the object to be sealed such as an organic EL element formed on a transparent substrate is suppressed, and electrodes and organic Deterioration of the layer can be effectively suppressed.
In the present specification, the water vapor transmission rate means a value measured by the method described in the examples.
Moreover, although the adhesive composition which is a forming material is the same as the adhesive agent layer which the gas-barrier laminated body (2) of this invention has, and the sheet-like article prescribed | regulated by said requirement (I), the said sheet-like article Although the thickness is specified as 50 μm, the thickness of the adhesive layer is not limited to 50 μm, and is appropriately set according to the application.

  Here, the thickness of the adhesive layer of the gas barrier laminates (1) and (2) of the present invention is appropriately set according to the application, but is preferably 2 to 50 μm, more preferably 5 to 40 μm, More preferably, it is 10-30 micrometers.

The storage elastic modulus G ′ at 80 ° C. of the adhesive layer of the gas barrier laminates (1) and (2) of the present invention is preferably 0.3 MPa or less, more preferably 0.2 MPa or less, still more preferably 0. It is 1 MPa or less, more preferably 0.09 MPa or less.
The storage elastic modulus G ′ at 80 ° C. of the adhesive layer is 0.3 MPa or less, so the gas barrier laminate of the present invention is excellent in unevenness followability, and the sealing effect of suppressing deterioration of the object to be sealed is high. It can be a material.
Further, from the viewpoint of handleability, the storage elastic modulus G ′ at 80 ° C. of the adhesive layer is usually 0.001 MPa or more, preferably 0.005 MPa or more, and more preferably 0.01 MPa or more.
In addition, in this specification, storage-elastic-modulus G 'of an adhesive bond layer means the value measured by the method as described in an Example.

The adhesive layer of the gas barrier laminates (1) and (2) of the present invention preferably has thermosetting properties. Such an adhesive layer is extremely excellent in adhesive strength after curing.
The conditions for thermally curing the adhesive layer are not particularly limited, but the heating temperature is usually 80 to 200 ° C. (preferably 90 to 150 ° C.), and the heating time is usually 30 minutes to 12 hours (preferably 1) ~ 6 hours).

The adhesive composition which is a formation material of the adhesive bond layer which the gas-barrier laminate (1) of the present invention has is a component other than the components (A) and (B) as long as the effect of the present invention is not impaired. You may contain.
As such a component, the adhesive composition may further contain one or more selected from a tackifier (C), an imidazole curing catalyst (D), and a silane coupling agent (E). Preferably, it is more preferable to further include components (C), (D) and (E).

  Moreover, if the adhesive composition which is a formation material of the adhesive bond layer which the gas-barrier laminated body (2) of this invention has is prepared so that the said requirements (I) may be satisfy | filled, other than a component (B) The component (B) may be contained together with the component (B), the polyolefin resin (A) may be contained, and even if it contains one or more selected from the components (C) to (E) described above. Good.

  In the adhesive composition which is a formation material of the adhesive layer which the gas barrier laminates (1) and (2) of the present invention have, as the total content of the components (A) and (B), the adhesive composition Based on the total amount (100% by mass) of the active ingredients of the present invention, preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass or more, particularly preferably 70 It is not less than mass%, and usually not more than 100 mass%, preferably not more than 99.9 mass%.

The adhesive composition which is a formation material of the adhesive bond layer which the gas-barrier laminates (1) and (2) of the present invention have, components (A), (B), (C), (D) and (E) The total content of these is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass with respect to the total amount (100% by mass) of the active components of the adhesive composition. %, Still more preferably 90 to 100% by mass.
In the present specification, the active ingredient of the adhesive composition refers to the ingredient contained in the adhesive composition except for the diluting solvent which is not involved in the physical properties.
Hereinafter, each component contained in the adhesive composition which is a formation material of the adhesive bond layer which the gas barrier laminates (1) and (2) of the present invention have will be described in detail.

<Component (A): Polyolefin resin>
By containing the polyolefin resin (A) in the adhesive composition to be the material for forming the adhesive layer, the water vapor transmission rate of the adhesive layer to be formed can be reduced, and sealing is performed via the adhesive layer. It is possible to effectively suppress the entry of water into the stop.

In the present invention, a polyolefin resin refers to a polymer having a repeating unit derived from an olefin monomer.
In the present invention, the polyolefin resin may be a polymer composed only of repeating units derived from an olefin monomer, or may be an olefin monomer together with a repeating unit derived from an olefin monomer. It may be a copolymer having a repeating unit derived from a monomer other than the above.

The above-mentioned olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene or 1-hexene, and still more preferably ethylene or propylene.
As monomers other than an olefin type monomer, vinyl acetate, (meth) acrylic acid ester, styrene etc. are mentioned, for example.

Specific polyolefin resins include, for example, very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP) Ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, poly Isobutylene, polyisoprene and the like can be mentioned.
In the present specification, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the other similar terms are also the same.
The polyolefin resin (A) may be used alone or in combination of two or more.

Moreover, in one aspect of the present invention, the component (A) preferably contains a modified polyolefin resin (A1).
The adhesive composition containing the modified polyolefin resin (A1) is excellent in adhesive strength and can easily form an adhesive layer having a relatively thin film thickness.

The component (A) may be used in combination with the modified polyolefin resin (A1) and the non-modified polyolefin resin, or may be composed of only the modified polyolefin resin (A1).
From the viewpoint of making the adhesive composition excellent in adhesive strength and easy to form an adhesive layer having a relatively thin film thickness, the content ratio of the component (A1) is the content of the component (A) contained in the adhesive composition. The total amount (100% by mass) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.

In the present invention, the modified polyolefin resin is a polyolefin resin having a functional group obtained by subjecting the above-mentioned polyolefin resin as a precursor to a modification treatment using a modifier having a functional group.
The modifier used for the modification | denaturation process of polyolefin resin should just be a compound which has a functional group, ie, the group which can be contributed to the crosslinking reaction mentioned later, in a molecule | numerator.
As the functional group, a carboxyl group, a group derived from a carboxylic acid anhydride (-CO-O-CO-), a carboxylic acid ester group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group And an isocyanate group, an acetyl group, a thiol group, an ether group, a thioether group, a sulfone group, a phosphonic group, a nitro group, a urethane group, a halogen atom and the like.
Among these, a carboxyl group, a group derived from a carboxylic acid anhydride, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, or an isocyanate group is preferable, and a group derived from a carboxylic acid anhydride or alkoxysilyl Groups are more preferred, and groups derived from carboxylic acid anhydrides are even more preferred.
The modifier used may be a compound having two or more functional groups in the molecule.

  The modified polyolefin resin (A1) is an acid-modified polyolefin resin or silane-modified from the viewpoint of forming an adhesive composition which is excellent in adhesive strength and low in water vapor transmission rate and easily forms an adhesive layer having high gas barrier properties. Polyolefin resins are preferable, and acid-modified polyolefin resins are more preferable.

  In the present invention, the acid-modified polyolefin resin refers to a polyolefin resin grafted and modified with an acid having a functional group which is a modifier. For example, those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid and / or an anhydride of an unsaturated carboxylic acid to introduce a carboxyl group and / or a group derived from a carboxylic acid anhydride (graft modification) are mentioned.

Examples of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids to be reacted with a polyolefin resin include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride Examples thereof include acids, glutaconic anhydride, citraconic anhydride, aconitic acid anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride and the like.
These may be used alone or in combination of two or more.
Among these, maleic anhydride is preferable from the viewpoint of forming an adhesive composition that is excellent in adhesive strength, low in water vapor transmission rate, and easy to form an adhesive layer having high gas barrier properties.

  The blending amount of the unsaturated carboxylic acid and / or the anhydride of the unsaturated carboxylic acid to be reacted with the polyolefin resin is excellent in adhesive strength and has a low water vapor transmission rate and an adhesive composition which easily forms an adhesive layer having high gas barrier properties. From the viewpoint of the product, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the polyolefin resin before modification. It is a department.

In the present invention, a commercially available product can also be used as the acid-modified polyolefin resin.
Examples of commercially available acid-modified polyolefin-based resins include Admar (registered trademark) (Mitsui Chemical Co., Ltd.), Unistoll (registered trademark) (Mitsui Chemical Co., Ltd.), BondyRam (Polyram), orevac (registered trademark) Trademark (made by ARKEMA), Modic (trademark) (made by Mitsubishi Chemical Corporation), etc. are mentioned.

  Further, in the present invention, a silane-modified polyolefin resin refers to a polyolefin resin grafted and modified with an unsaturated silane compound which is a modifier. That is, the silane-modified polyolefin resin has a structure in which an unsaturated silane compound which is a side chain is graft-copolymerized to a polyolefin resin which is a main chain.

As the unsaturated silane compound to be reacted with the polyolefin resin, a vinylsilane compound is preferable. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane And vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane and the like.
These unsaturated silane compounds may be used alone or in combination of two or more.
In addition, the conditions in the case of graft-polymerizing an unsaturated silane compound to the polyolefin resin which is a principal chain should just adopt the usual method of graft polymerization well-known.

  The compounding amount of the unsaturated silane compound to be reacted with the polyolefin resin is excellent in adhesive strength and low in water vapor transmission rate, and from the viewpoint of forming an adhesive composition having a high gas barrier property and easy to form an adhesive layer, polyolefin before modification Preferably it is 0.1-10 mass parts with respect to 100 mass parts of resin, More preferably, it is 0.3-7 mass parts, More preferably, it is 0.5-5 mass parts.

  Specific examples of the silane-modified polyolefin resin include silane-modified polyethylene resin and silane-modified ethylene-vinyl acetate copolymer, silane-modified low density polyethylene, silane-modified ultra-low density polyethylene, silane-modified linear resin Preferred are silane modified polyethylene resins such as low density polyethylene.

In the present invention, commercially available silane-modified polyolefin resins can also be used.
Examples of commercially available silane-modified polyolefin resins include, but are not limited to, Linkron (registered trademark) (Mitsubishi Chemical Co., Ltd.) and the like, but low density polyethylene-based Lyndon and linear low density polyethylene-based Linkron , Ultra-low density polyethylene-based Lyndon and ethylene-vinyl acetate copolymer-based Lyndron are preferred.

As a weight average molecular weight (Mw) of a polyolefin resin (A), it is excellent in adhesive strength and has a low water vapor transmission rate, and an adhesive composition having a high gas barrier property is easily formed into an adhesive composition, and a sheet From the viewpoint of forming an adhesive composition which is excellent in shape-retaining property capable of maintaining its shape when formed into a shape, preferably 10,000 to 2,000,000, more preferably 20,000 to 1, 500,000, more preferably 25,000 to 250,000, still more preferably 30,000 to 150,000.
Even if the content of the polyolefin resin (A) in the adhesive composition is high when the weight average molecular weight of the polyolefin resin (A) is in the above range, a sheet formed from the adhesive composition The shape is easy to maintain.

  In the present specification, the weight average molecular weight (Mw) is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent, and specifically, in Examples. It is a value measured based on the method described.

  The polyolefin resin (A) is a solid at normal temperature (25 ° C.) from the viewpoint of forming an adhesive composition that can maintain its shape when formed into a sheet shape. Is preferred.

  The content of the component (A) is preferably 5 to 90% by mass, more preferably 15 to 80% by mass, still more preferably 23 to 70, based on the total amount (100% by mass) of the active components of the adhesive composition. % By mass, more preferably 30 to 60% by mass.

<Component (B): Multifunctional Epoxy Compound>
The adhesive composition used as the formation material of an adhesive bond layer contains a polyfunctional epoxy compound (B).
By containing a polyfunctional epoxy compound (B), the interlayer adhesion between the adhesive layer to be formed and the gas barrier layer containing the polymer compound and subjected to the modification treatment can be made favorable.
In addition, a polyfunctional epoxy compound (B) may be used independently, and may use 2 or more types together.

In the present invention, the polyfunctional epoxy compound refers to a compound having at least two or more epoxy groups in the molecule.
The component (B) is a bifunctional resin having two or more epoxy groups, from the viewpoint of further improving the interlayer adhesion between the adhesive layer to be formed and the polymer compound and the gas barrier layer subjected to the modification treatment. Epoxy compounds are preferred.

As a bifunctional epoxy compound, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac Epoxy compounds such as epoxy resin (for example, phenol novolac epoxy resin, cresol novolac epoxy resin, brominated phenol novolac epoxy resin); hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether Alicyclic epoxy compounds such as hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1,6-hexanediyl Diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane, dimethylol tricyclode Aliphatic epoxy compounds such as candiglycidyl ether can be mentioned.
Among these, the polyfunctional epoxy compound (B) is preferably at least one selected from polyfunctional alicyclic epoxy compounds and polyfunctional aliphatic epoxy compounds.

  The molecular weight of the polyfunctional epoxy compound (B) is preferably 200 or more from the viewpoint of further improving the interlayer adhesion between the adhesive layer to be formed and the polymer compound and the gas barrier layer subjected to the modification treatment. More preferably, it is 300-4500, still more preferably 500-4000, still more preferably 600-3500.

  The epoxy equivalent of the polyfunctional epoxy compound is preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, and still more preferably 150 to 300 g / eq or less.

The content of the component (B) is a gas barrier layer that includes an adhesive layer and a polymer compound to be formed per 100 parts by mass of the component (A) contained in the adhesive composition, and is subjected to a modification treatment In order to further improve the adhesion between the layers, the content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and storage of the formed adhesive layer at 80 ° C. From the viewpoint of adjusting the elastic modulus G ′ to be low and forming a gas barrier laminate having good conformity to irregularities, it is more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, still more preferably 65 parts by mass or more is there.
In addition, from the viewpoint of facilitating formation of an adhesive layer excellent in adhesive strength, the content of component (B) is preferably 200 parts by mass with respect to 100 parts by mass of component (A) contained in the adhesive composition. The amount is more preferably 180 parts by mass or less, still more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less.

<Component (C): tackifier>
The adhesive composition preferably further contains a tackifier (C) from the viewpoint of making the shape-retaining property of the formed adhesive layer better.

As the tackifier (C), for example, rosin-based resins such as polymerized rosin, polymerized rosin ester, rosin derivative and the like; polyterpene resins, aromatic modified terpene resins and hydrogenated products thereof, and terpene resins such as terpene phenol resins; Indene resins; petroleum resins such as aliphatic petroleum resins, aromatic petroleum resins and their hydrides, aliphatic / aromatic copolymer petroleum resins, etc .; styrene or substituted styrene polymers; α-methylstyrene homopolymer resins Copolymers of α-methylstyrene and styrene, copolymers of styrenic monomers and aliphatic monomers, copolymers of styrenic monomers, α-methylstyrene and aliphatic monomers, styrenic monomers Styrene-based resins such as homopolymers, copolymers of styrene-based monomers and aromatic-based monomers, and the like.
These tackifiers (C) may be used alone or in combination of two or more.
Among these, as a component (C), a styrene resin is preferable, and a copolymer of a styrene monomer and an aliphatic monomer is more preferable.

The softening point of the tackifier (C) is preferably 80 ° C. or higher, more preferably 85 to 170 ° C., still more preferably, from the viewpoint of further improving the shape retention and adhesive strength of the adhesive layer to be formed. 90 to 150 ° C.
In the present specification, the softening point means a value measured according to JIS K 5902.
When two or more types of tackifiers are used, it is preferable that the weighted average of the softening points of the plurality of tackifiers belongs to the above range.

  The content of the component (C) is preferably 1 to 200 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of further improving the shape retentivity of the adhesive layer formed. It is 150 parts by mass, more preferably 15 to 100 parts by mass, and still more preferably 20 to 80 parts by mass.

<Component (D): imidazole curing catalyst>
The adhesive composition preferably further contains an imidazole-based curing catalyst (D) from the viewpoint of forming an adhesive layer in which the adhesive strength in a high temperature environment is further improved.

As the imidazole based curing catalyst (D), 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, Examples include 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.
These imidazole curing catalysts (D) may be used alone or in combination of two or more.
Among these, 2-ethyl-4-methylimidazole is preferable as the component (D).

  The content of the component (D) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of forming an adhesive layer in which the adhesive strength in a high temperature environment is further improved. More preferably, it is 0.2-5 mass parts, More preferably, it is 0.3-2.5 mass parts.

<Component (E): Silane Coupling Agent>
The adhesive composition preferably further contains a silane coupling agent (E) from the viewpoint of facilitating the formation of an adhesive layer having excellent adhesive strength under both normal temperature and high temperature environments.
In addition, when the adhesive composition contains a silane coupling agent, the interlayer adhesion between the formed adhesive layer and the gas barrier layer subjected to the modification treatment is further improved.

As the silane coupling agent (E), an organosilicon compound having at least one alkoxysilyl group in the molecule is preferable from the above viewpoint.
Specific examples of the silane coupling agent (E) include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy Silicon compounds having an epoxy structure such as silane, glycidoxyoctyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc .; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl)- Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3-isocyanatepropyltriethoxysilane; etc. It can be mentioned.
These silane coupling agents (E) may be used alone or in combination of two or more.

  The content of the component (E) makes it easy to form an adhesive layer having excellent adhesive strength under both normal temperature and high temperature environments, and interlayer adhesion between the formed adhesive layer and the gas barrier layer From the viewpoint of improving the properties, preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and still more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of component (A) is there.

<Other additives>
The adhesive composition may contain other additives other than the components (A) to (E) described above as long as the effects of the present invention are not impaired.
The other additives are appropriately selected according to the application, but for example, UV absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, etc. And additives.
These additives may be used alone or in combination of two or more.

The adhesive composition may further contain a dilution solvent from the viewpoint of improving moldability.
The dilution solvent can be appropriately selected from organic solvents, but specifically, aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane and the like; .
These solvents may be used alone or in combination of two or more.
The content of the solvent can be appropriately set in consideration of coating properties and the like.

<Method of forming adhesive layer>
As a method of forming an adhesive layer, for example, a method of applying an adhesive composition on a release treated surface of a release film to form a coating film, drying the coating film to form an adhesive layer, and the like Be
Examples of the method of applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
In addition, from the viewpoint of improving the coatability, it is preferable to add the above-described dilution solvent to the adhesive composition to form a solution.
As a drying condition when drying a coating film, for example, it is preferable to perform the drying process for 30 seconds to 5 minutes at 80-150 degreeC normally.

[Gas barrier layer]
The gas barrier layer of the gas barrier laminate of the present invention is a layer that contains a polymer compound and has been subjected to a modification treatment. The gas barrier layer has excellent gas barrier properties and is excellent in flexibility, so that it can be a gas barrier laminate excellent in resistance to bending.
The thickness of the gas barrier layer is preferably 50 to 300 nm, more preferably 50 to 200 nm.
The gas barrier layer of the gas barrier laminate of the present invention has sufficient gas barrier properties even when the thickness is nano order.

Examples of the polymer compound contained in the gas barrier layer include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compound, polyimide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester And polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer and the like.
These high molecular weight compounds may be used alone or in combination of two or more.
Among these, as a polymer compound contained in the gas barrier layer, a silicon-containing polymer compound is preferable and a polysilazane compound is more preferable from the viewpoint of forming a gas barrier laminate having excellent gas barrier properties.
The number average molecular weight of the polysilazane compound is preferably 100 to 50,000.

The polysilazane compound is a polymer having a repeating unit containing -Si-N- bond (silazane bond) in the molecule, and specifically, a polymer having a repeating unit represented by the following general formula (1) Is preferred.

In the above general formula (1), n represents the number of repeating units and represents an integer of 1 or more.
Each of Rx, Ry and Rz independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted Represents an aryl group or an alkylsilyl group having a group.
Among these, as Rx, Ry and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is more preferable.
The polymer compound contained in the gas barrier layer may be an inorganic polysilazane in which all of Rx, Ry and Rz in the general formula (1) are hydrogen atoms, and at least one of Rx, Ry and Rz is hydrogen. It may be an organic polysilazane which is a group other than an atom.

The polysilazane compounds may be used alone or in combination of two or more.
Moreover, a polysilazane modified product can also be used as a polysilazane type compound, Moreover, a commercial item can also be used.

The gas barrier layer may further contain other components in addition to the above-described polymer compound as long as the effects of the present invention are not impaired.
Other components include, for example, curing agents, other polymers, anti-aging agents, light stabilizers, flame retardants and the like.
The content of the polymer compound in the gas barrier layer is preferably 50 to 100% by mass with respect to the total amount (100% by mass) of the components in the gas barrier layer from the viewpoint of forming a gas barrier layer having more excellent gas barrier properties. More preferably, it is 70-100 mass%, More preferably, it is 80-100 mass%.

  As a method for forming the gas barrier layer, for example, a known device such as a spin coater, a knife coater, or a gravure coater for a solution for forming a gas barrier layer containing at least one polymer compound, optionally other components, and a solvent etc. The method of apply | coating using and forming a coating film, and drying and forming the said coating film is mentioned.

Examples of the modification treatment of the gas barrier layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment and the like.
The ion implantation process is a method of modifying the gas barrier layer by implanting ions into the gas barrier layer as described later.
Plasma treatment is a method of exposing the gas barrier layer to plasma to modify the gas barrier layer. For example, plasma treatment can be performed according to the method described in JP-A-2012-106421.
The ultraviolet irradiation treatment is a method of irradiating the gas barrier layer with ultraviolet light to modify the gas barrier layer. For example, an ultraviolet-ray modification process can be performed according to the method as described in Unexamined-Japanese-Patent No. 2013-226757.
Among these, from the viewpoint that the gas barrier layer can be formed more efficiently by modifying the inside of the gas barrier layer without roughening the surface and forming the gas barrier layer having more excellent gas barrier properties, ion implantation treatment preferable.

Examples of ions to be implanted into the gas barrier layer in the ion implantation treatment include ions of a rare gas such as argon, helium, neon, krypton and xenon; fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, Ions such as sulfur; Ions of alkane-based gases such as methane and ethane; Ions of alkenes such as ethylene and propylene; Ions of alkadiene-based gases such as pentadiene and butadiene; Ions of alkyne-based gases such as acetylene Ions of aromatic hydrocarbon gases such as benzene and toluene; ions of cycloalkane gases such as cyclopropane; ions of cycloalkene gases such as cyclopentene; metal ions; ions of organosilicon compounds; It can be mentioned.
These ions may be used alone or in combination of two or more.
Among these, ions of a rare gas such as argon, helium, neon, krypton and xenon are preferable, from the viewpoint that ions can be more easily injected and a gas barrier layer having particularly excellent gas barrier properties can be obtained. Argon ion is more preferred.

The method for implanting ions is not particularly limited. For example, a method of irradiating ions (ion beam) accelerated by an electric field, a method of injecting ions in plasma (ions of plasma generating gas), etc. may be mentioned, and a gas barrier layer is easily obtained. The method of implanting ions is preferred.
Ions in the plasma are generated, for example, by generating a plasma in an atmosphere containing a plasma generating gas, and applying a negative high voltage pulse to the layer into which the ions are injected, ions (positive ions) in the plasma. Can be implanted into the surface of the layer into which the ions are implanted.

[Base material layer]
As a base material layer which the gas-barrier laminated body of this invention has, a metal foil, a resin film, a thin film glass etc. are mentioned, for example, A resin film is preferable.
As a resin component which constitutes a resin film, for example, polyimide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, Acrylic resin, cycloolefin polymer, aromatic polymer, polyurethane polymer and the like can be mentioned.
These resin components may be used alone or in combination of two or more.

When the base material layer is made of a resin film, the surface of the resin film is subjected to easy adhesion treatment by an oxidation method, an unevenness forming method, or the like from the viewpoint of improving the adhesion with the layer laminated on the resin film. It is preferable to apply.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet process), hot air treatment, ozone, and ultraviolet light irradiation treatment. Examples of the surface roughening method include sand blast method and solvent treatment method. Etc.

  The thickness of the substrate layer is not particularly limited, but is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and still more preferably 5 to 100 μm from the viewpoint of easy handling.

[Primer layer]
In the gas barrier laminate of the present invention, from the viewpoint of further improving the adhesion between the base layer and the gas barrier layer, a primer layer is provided between the base layer and the gas barrier layer as one of adhesion facilitating means. It is also good.
As said primer layer, the layer which hardened the composition containing an ultraviolet curable compound is mentioned, for example. The composition containing the ultraviolet curable compound may contain an inorganic filler such as silica particles.
The thickness of the primer layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[Peeling film]
As a peeling film which the gas barrier laminate of the present invention has, a conventionally known one can be used, and for example, one having a peeling layer subjected to a peeling treatment with a peeling agent on a peeling film substrate can be mentioned. .
Examples of substrates for release films include paper substrates such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; polyethylene terephthalate resin, polybutylene terephthalate resin And plastic films formed from polyethylene naphthalate resin, polypropylene resin, polyethylene resin and the like.
Examples of release agents include silicone resins, olefin resins, isoprene resins, rubber elastomers such as butadiene resins, long chain alkyl resins, alkyd resins, fluorine resins, and the like.

[Sealing body]
The sealed body of the present invention is obtained by sealing an object to be sealed with the gas barrier laminate of the present invention.
The sealing body of the present invention includes, for example, a transparent substrate, an element (object to be sealed) formed on the transparent substrate, and a gas barrier laminate which is a sealing material for sealing the element. Is provided.

The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high visible light transmittance. In addition, a material having a high blocking performance to block moisture and gas from the outside of the element and having excellent solvent resistance and weather resistance is preferable.
Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, Transparent plastics, such as polystyrenes, polyarylates, polysulfones, and polyolefins, and the gas barrier film mentioned above;
The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of the light transmittance and the performance of blocking the inside and outside of the device.

As an object to be sealed, an organic EL element, an organic EL display element, a liquid crystal display element, a solar cell element and the like can be mentioned.
That is, it is preferable that the sealing body of this invention seals an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element with the gas-barrier laminated body of this invention.

The manufacturing method of the sealing body of this invention is not specifically limited. For example, after the adhesive layer of the gas barrier laminate of the present invention is stacked on an object to be sealed, the adhesive layer and the object to be sealed are adhered by heating.
Then, the adhesive layer is cured to produce the sealed body of the present invention.

  The bonding conditions for bonding the adhesive layer of the gas barrier laminate and the object to be sealed are not particularly limited. The bonding temperature is, for example, 23 to 100 ° C., preferably 40 to 80 ° C. This adhesion process may be performed while applying pressure. As the curing conditions for curing the adhesive layer, the conditions described above can be used.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
In addition, the molecular weight of modified polyolefin resin and acrylic resin is the value measured by the following method.
<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the modified polyolefin resin and the weight average molecular weight (Mw) of the acrylic resin are measured using a gel permeation chromatograph (GPC) apparatus (product name "HLC-8020" manufactured by Tosoh Corporation). It measured under the following conditions and used the value measured by standard polystyrene conversion.
(Measurement condition)
・ Column: “TSK guard column HXL-L”, “TSK gel G2500 HXL”, “TSK gel G2000 HXL”, “TSK gel G1000 HXL” (all manufactured by Tosoh Corporation) • Column temperature: 40 ° C.
-Developing solvent: tetrahydrofuran-Flow rate: 1.0 mL / min

Examples 1-2, comparative examples 1-2
(1) Preparation of adhesive composition Each component shown below is added by the compounding quantity (active ingredient ratio) of Table 1, and it dilutes with methyl ethyl ketone, and in Examples 1-2 and comparative example 1 An adhesive composition having an active ingredient concentration of 30% by mass was prepared, and in Comparative Example 2, an adhesive composition having an active ingredient concentration of 35% by mass was prepared.
The details of each component used are as follows.
Modified polyolefin resin: manufactured by Mitsui Chemicals, Inc., product name "Unistol H-200", acid-modified α-olefin polymer, weight average molecular weight (Mw) = 52,000.
Acrylic resin: copolymer of butyl acrylate (BA) and acrylic acid (AAc), BA / AAc = 90/10, weight average molecular weight (Mw) = 6500.
Polyfunctional epoxy compound: manufactured by Kyoeisha Chemical Co., Ltd., product name "Epolite 4000", hydrogenated bisphenol A diglycidyl ether, epoxy equivalent = 215 to 245 g / eq, molecular weight = 800.
-Tackifier: Mitsui Chemicals Co., Ltd. make, product name "FTR6100", The copolymer of a styrene-type monomer and an aliphatic type monomer, Softening point = 95 degreeC.
-Imidazole-based curing catalyst: manufactured by Shikoku Kasei Kogyo Co., Ltd., product name "Cuazole 2E4MZ", 2-ethyl-4-methylimidazole.
-Silane coupling agent: Shin-Etsu Chemical Co., Ltd. product name "KBM-4803", glycidoxy octyl trimethoxysilane.

(2) Formation of adhesive layer The prepared adhesive composition is applied on the release-treated surface of a release film (Lintech Co., Ltd., product name "SP-PET 382150") to form a coating, and the coating Dried at 100.degree. C. for 2 minutes to form a 12 .mu.m thick adhesive layer.
In addition, a laminate having a 50 μm-thick adhesive layer formed on a release film was also prepared as described above separately for measuring the water vapor transmission rate of the adhesive layer.

(3) Formation of gas barrier layer An ultraviolet-curable acrylate resin composition (A product made by Toyobo Co., Ltd., product name "PET50A4300") having a thickness of 50 μm on which both sides have been subjected to easy adhesion treatment The product name “OPSTAR Z7530” manufactured by JSR Corporation was applied using Meyer bar to form a coating, and the coating was dried at 70 ° C. for 1 minute. Then, using a non-electrode UV lamp system (made by Heraeus Co., Ltd.), ultraviolet rays are irradiated at an illuminance of 250 mW / cm ² and a light quantity of 170 mJ / cm ² to cure the coating film, and a primer layer having a thickness of 1000 nm is obtained. It formed.
Then, on the formed primer layer, a coating agent having a solid content concentration of 10% by mass mainly composed of perhydropolysilazane (product name “Aquamica NL 110-20” manufactured by Merck Performance Materials, a solvent: xylene), Using a spin coater (Mikasa Co., Ltd., product name “MS-A200”), a coating was formed at a rotational speed of 3000 rpm and a rotational time of 30 seconds to form a coating. And the said coating film was dried at 120 degreeC for 2 minutes, and the polysilazane layer comprised from the polysilazane of thickness 150 nm was formed on the said primer layer.
Subsequently, the surface of the polysilazane layer thus formed was reformed by plasma ion implantation under the following conditions using a plasma ion implantation apparatus to form a gas barrier layer having a thickness of 150 nm.
(Processing conditions for plasma ion implantation)
・ Chamber internal pressure: 0.2Pa
-Plasma generated gas: Argon-Gas flow rate: 100 sccm
・ RF output: 1000W
・ RF frequency: 1000 Hz
· RF pulse width: 50 μs · RF delay: 25 ns · DC voltage: -6 kV
・ DC frequency: 1000 Hz
· DC pulse width: 5 μs · DC delay: 50 μs · Duty ratio: 0.5%
Processing time: 200 seconds Further, on the formed gas barrier layer, the formation of a 150 nm-thick gas barrier layer is further repeated three times in the same manner as above, and four 150 nm-thick gas barrier layers are laminated. A gas barrier film having a gas barrier layer with a thickness of 600 nm was obtained.

(4) Preparation of gas barrier laminate The surface of the adhesive layer with a thickness of 12 μm formed in the above (2) and the surface of the gas barrier layer with a thickness of 600 nm of the gas barrier film produced in the above (3) It bonded together at 60 degreeC using the laminator, and produced the gas-barrier laminated body.

  The following physical property values were measured and evaluated using the above-mentioned adhesive bond layer and gas barrier laminate obtained in Examples and Comparative Examples. The results are shown in Table 1.

[Water vapor permeability of adhesive layer]
The peelable film is removed from the laminate of the peelable film and the adhesive layer having a thickness of 50 μm prepared in Examples or Comparative Examples, and only the adhesive layer is used as a test sample to determine the gas permeability measurement device The water vapor transmission rate of the adhesive layer was measured using (manufactured by mocon, product name "PERMATRAN").

[Storage elastic modulus G 'of adhesive layer]
A plurality of adhesive layers formed in Examples and Comparative Examples were stacked, and heat compression was performed at 60 ° C. using a heat laminator to obtain a multilayer of adhesive layers having a thickness of 1 mm.
Before curing in a temperature range of 23 to 150 ° C., using a viscoelasticity measuring apparatus (product name: “Physica MCR 301”, product name: “Physica MCR 301”) with a double layer of this adhesive layer as a test sample Storage elastic modulus G ′ of the multilayer body of the adhesive layer was measured. The measured values of storage modulus G ′ at 80 ° C. are shown in Table 1.

[Interlayer adhesion evaluation]
The gas barrier laminate prepared in the examples and comparative examples is cut into a size of 25 mm long × 300 mm wide, the release film is removed, the surface of the exposed adhesive layer is attached to a glass plate, and a heat laminator is used. The sample was crimped at 60 ° C. to prepare a test sample. Then, the test sample was heated at 100 ° C. for 2 hours to cure the adhesive layer, and then allowed to stand at 23 ° C. for 24 hours.
Furthermore, when the gas barrier laminate is peeled off from the glass plate under the condition of peeling angle 180 ° after leaving still for 168 hours under the environment of temperature 85 ° C. and 85% RH (relative humidity), adhesion to the glass plate The presence or absence of transfer of the agent layer was confirmed, and the interlayer adhesion between the gas barrier layer and the adhesive layer was evaluated according to the following criteria.
A: Transfer of the adhesive layer to the glass plate was not confirmed.
F: Transfer of the adhesive layer to the glass plate was confirmed.

[Convexity tracking evaluation]
A small piece of polyethylene terephthalate having a thickness of 10 μm was placed on a glass substrate as a pseudo device. Then, the release film of the gas barrier laminate prepared in the example and the comparative example is removed, and the exposed adhesive layer is completely covered with the pseudo device on the glass substrate, thereby forming the adhesive layer on the glass substrate and the pseudo device. And sealed at 80 ° C. using a heat laminator, and then subjected to pressure treatment at 80 ° C. and 0.5 MPa for 20 minutes. Then, the adhesive layer was cured by heating at 100 ° C. for 2 hours.
The boundary portion between the pseudo device and the adhesive layer after curing is observed in plan view using an optical microscope, and as described below, gas barrier lamination is performed depending on the presence or absence of a gap between the pseudo device and the adhesive layer. The unevenness followability of the body was evaluated.
A: Since there is no gap between the pseudo device and the adhesive layer, the unevenness followability is good.
F: Since a gap is confirmed between the pseudo device and the adhesive layer, the unevenness followability is inferior.

The adhesive layer of the gas barrier laminate prepared in Examples 1 and 2 is excellent in interlayer adhesion to the gas barrier layer and has a low water vapor transmission rate, so an object to be sealed with water via the adhesive layer is obtained. It can be said that the sealing material is excellent in the effect of suppressing the infiltration of
On the other hand, the gas barrier laminate produced in Comparative Example 1 resulted in poor interlayer adhesion between the adhesive layer and the gas barrier layer.
Moreover, the adhesive bond layer which the gas-barrier laminated body produced by the comparative example 2 had the water vapor transmission rate became a very high value. Therefore, in Comparative Example 2, the test was completed without conducting other tests.

Claims (11)

A gas barrier layer containing a polymer compound and subjected to a modification treatment,
An adhesive layer formed from an adhesive composition containing a polyolefin resin (A) and a polyfunctional epoxy compound (B),
A gas barrier laminate having a configuration in which the gas barrier layer and the adhesive layer are directly laminated.   The gas barrier laminate according to claim 1, wherein the component (A) contains a modified polyolefin resin (A1).   The gas barrier laminate according to claim 2, wherein the component (A1) is an acid-modified polyolefin resin.   The gas barrier laminate according to any one of claims 1 to 3, wherein the storage elastic modulus G 'at 80 ° C of the adhesive layer is 0.3 MPa or less.   The gas barrier laminate according to any one of claims 1 to 4, wherein the content of the component (A) is 5 to 90% by mass with respect to the total amount of the active components of the adhesive composition.   The gas barrier according to any one of claims 1 to 5, wherein the content of the component (B) is 5 to 200 parts by mass with respect to 100 parts by mass of the component (A) contained in the adhesive composition. Sex stacks.   The gas barrier laminate according to any one of claims 1 to 6, wherein the adhesive composition further contains a tackifier (C).   The gas barrier laminate according to any one of claims 1 to 7, wherein the adhesive composition further contains an imidazole-based curing catalyst (D).   The gas barrier laminate according to any one of claims 1 to 8, wherein the adhesive composition further contains a silane coupling agent (E). A gas barrier layer containing a polymer compound and subjected to a modification treatment,
Having an adhesive layer formed of an adhesive composition containing the polyfunctional epoxy compound (B) and satisfying the following requirement (I),
A gas barrier laminate having a configuration in which the gas barrier layer and the adhesive layer are directly laminated.
Requirement (I): The water vapor transmission rate of the 50 μm-thick sheet material formed from the adhesive composition is 200 g / m ² / day or less.   The sealing body formed by sealing an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element by the gas-barrier laminated body as described in any one of Claims 1-10.