JPWO2020067488A1 - Gas barrier laminate - Google Patents

Abstract

A gas-barrier laminated body having a laminated structure in which a curable adhesive layer, a gas barrier film, and a protective film are arranged in this order, and the gas-barrier laminated body is used as the curable adhesive layer. As a bonding surface, the gas barrier laminate and the glass plate are adhered to each other by pressing them against a glass plate under the following condition (α), and then peeled off under the following condition (β). Other conditions are JIS Z0237. : The adhesive force a between the glass plate and the curable adhesive layer and the adhesive force b between the gas barrier film and the protective film, which are measured in accordance with 2000, are expressed by the following formulas ( A gas barrier laminated body satisfying 1) was prepared. a> b ... (1) Condition (α): Temperature 23 ° C., pressure 0.2 MPa, and speed 0.2 m / min Condition (β): After application, 24 in an environment of 23 ° C. and 50% relative humidity After leaving it for a while, peel it off at a peeling speed of 300 mm / min.

Description

The present invention relates to a gas barrier laminate.

In recent years, an organic EL element has attracted attention as a light emitting element capable of high-luminance light emission by low-voltage direct current drive.
However, the organic EL element has a problem that the light emitting characteristics tend to deteriorate with time. It is considered that this problem is caused by oxygen, moisture, etc. infiltrating into the inside of the organic EL element and deteriorating the electrode and the organic layer. Therefore, as a countermeasure against this problem, the organic EL element is sealed with a sealing material to prevent the infiltration of oxygen, moisture, and the like.
Specifically, a method of sealing an object to be sealed such as an organic EL element with a gas barrier sealing material having a layer structure has been proposed. Patent Document 1 describes a technique for sealing an organic EL element by using a sealing film in which a gas barrier film is laminated on an adhesive film.

JP-A-2007-197517

An object to be sealed, which needs to be prevented from being deteriorated by oxygen, moisture, etc., such as an electronic device such as an organic EL element, has an adhesive layer like a sealing film having a layer structure described in Patent Document 1. It may be sealed by a gas barrier laminate having a laminated structure in which a gas barrier film is laminated.

By the way, the process of storage and transportation until the gas barrier laminated body is used, the process of sealing the object to be sealed with the gas barrier laminated body to prepare the sealed body, and the processing and transportation of the sealed body, etc. In the process of, the gas barrier film is placed on the outermost surface. Therefore, the gas barrier film may be scratched or cracked, and the gas barrier property of the gas barrier film may be deteriorated. Further, when the object to be sealed is a light emitting element such as an organic EL element and used for a display or the like, if the gas barrier film is scratched or cracked, the scratch or crack becomes a defect and a bright spot or the like is generated. It may be.

Therefore, the present inventors have performed processes such as storage and transportation until the gas barrier laminate is used, a process of sealing the object to be sealed with the gas barrier laminate to prepare a sealed body, and the sealing. In order to prevent the gas barrier film from being scratched or cracked in the process of processing and transporting the body, it was considered to protect the entire surface of the gas barrier film with a protective film and peel off the protective film at a desired timing. .. The desired timing means, for example, a timing at which protection of the gas barrier film is no longer necessary, a timing at which the gas barrier film needs to be exposed, and the like.
However, it has become clear that when the protective film is peeled off after sealing the object to be sealed with the gas barrier laminate, a gap may be generated between the object to be sealed and the adhesive layer. If a gap is generated between the material to be sealed and the adhesive layer, oxygen, moisture, or the like may infiltrate through the gap, resulting in deterioration of the material to be sealed. In addition, the appearance is also poor. On the other hand, in the sealed body sealed by the gas barrier laminate, even if a gap between the sealed object and the adhesive layer does not occur, the sealed object can be sealed due to various factors. Oxygen, moisture, etc. may infiltrate and deteriorate the object to be sealed.

The present invention has been made in view of such a problem, and in the process of storage and transportation until the gas barrier laminate is used, the object to be sealed is sealed with the gas barrier laminate to form a sealed body. When the protective film is peeled off at a desired timing while preventing the gas barrier film from being scratched or cracked by the protective film in the process of manufacturing and the process of processing and transporting the sealed body, it is sealed. A gas barrier laminate that does not create a gap between the stop and the adhesive layer and that can improve the durability of the object to be sealed, and a method for manufacturing a seal using the gas barrier laminate. The purpose is to provide.

The present inventors have conducted diligent studies based on the above idea of protecting the gas barrier film with a protective film. As a result, the gas barrier laminate having a laminated structure in which the adhesive layer, the gas barrier film, and the protective film are arranged in this order is attached to the glass plate under specific conditions with the adhesive layer as the bonding surface. The above problems can be solved by adjusting the adhesive force between the glass plate and the adhesive layer and the adhesive force between the gas barrier film and the protective film so as to satisfy a specific relationship. I found that.

That is, the present invention relates to the following [1] to [14].
[1] An adhesive layer, a gas barrier film, and a protective film are gas barrier laminated bodies having a laminated structure arranged in this order.
The gas barrier laminate is pressed against a glass plate by a roller under the following condition (α) with the adhesive layer as a bonding surface, and after the gas barrier laminate and the glass plate are bonded, the following conditions (α) Peeling with β), the other conditions are measured in accordance with JIS Z0237: 2000, between the adhesive force a between the glass plate and the adhesive layer and between the gas barrier film and the protective film. A gas barrier laminate whose adhesive strength b satisfies the following formula (1).
a> b ... (1)
Condition (α): temperature 23 ° C., pressure 0.2 MPa, and speed 0.2 m / min
Condition (β): After application, the adhesive layer is allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then peeled off at a peeling speed of 300 mm / min. [2] The adhesive layer is a curable adhesive layer. , [1].
[3] The gas barrier laminate according to [2], wherein the curable adhesive layer is a layer formed from an adhesive composition containing a polyolefin resin (A).
[4] The gas barrier laminate according to [3], wherein the polyolefin-based resin (A) contains a modified polyolefin-based resin (A1).
[5] The curable adhesive layer contains a curable component (B), and the curable component (B) contains a polyfunctional epoxy compound (BL) that is liquid at 25 ° C. [2] to The gas barrier laminate according to any one of [4].
[6] The gas barrier laminate according to [5], wherein the weight average molecular weight (Mw) of the polyfunctional epoxy compound (BL) is 1,500 or more and 5,000 or less.
[7] The gas barrier laminate according to [5] or [6], wherein the content of the polyfunctional epoxy compound (BL) is 10 to 34% by mass based on the total amount of the adhesive composition.
[8] The gas barrier laminate according to any one of [1] to [7], wherein the gas barrier film has a base material layer and a gas barrier layer.
[9] The gas barrier laminate according to [8], wherein the base material layer has a resin film containing at least one selected from polycarbonate, a cycloolefin polymer, and a cycloolefin copolymer as a resin component.
[10] The gas barrier laminate according to [8] or [9], wherein the base material layer has a thickness of 30 μm or less.
[11] The gas barrier laminate according to any one of [8] to [10], wherein the gas barrier layer is a polymer layer containing a polymer compound and subjected to a modification treatment.
[12] The gas barrier laminate according to any one of [8] to [11], wherein the gas barrier layer and the adhesive layer are directly laminated.
[13] The gas barrier property according to any one of [1] to [12], wherein the protect film has a protect layer and an adhesive layer, and the adhesive layer is attached to the gas barrier film. Laminated body.
[14] A method for producing a sealed body, which comprises the following steps (1) and (2) in this order.
-Step (1): Step of attaching the gas barrier laminate according to any one of [1] to [13] to the object to be sealed with the adhesive layer as a bonding surface-Step (2): Protect Step of peeling the film from the gas barrier laminate

According to the present invention, a process of storage and transportation until the gas barrier laminated body is used, a process of sealing the object to be sealed with the gas barrier laminated body to prepare a sealed body, and a process of the sealed body. While preventing the gas barrier film from being scratched or cracked by the protective film in the process of processing and transportation, when the protective film is peeled off at a desired timing, it is between the object to be sealed and the adhesive layer. It is possible to provide a gas barrier laminated body in which no gap is generated and the durability of the object to be sealed can be improved, and a method for producing a sealed body using the gas barrier laminated body.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent, and are specific. Is a value measured based on the method described in Examples.

[Gas barrier laminate]
The gas-barrier laminate of the present invention is a gas-barrier laminate having a laminated structure in which an adhesive layer, a gas barrier film, and a protective film are arranged in this order.
Then, in the gas barrier laminate of the present invention, the gas barrier laminate is pressed against the glass plate by a roller under the following condition (α) with the adhesive layer as the bonding surface, and the gas barrier laminate and the glass plate are formed. Is peeled off under the following condition (β), and the other conditions are the adhesive strength a between the glass plate and the adhesive layer, and the gas barrier film and the protective film, which are measured in accordance with JIS Z0237: 2000. The adhesive force b between and the above is adjusted so as to satisfy the following formula (1).
a> b ... (1)
Condition (α): temperature 23 ° C., pressure 0.2 MPa, and speed 0.2 m / min
Condition (β): After application, the glass is allowed to stand at 23 ° C. and a relative humidity of 50% for 24 hours, and then peeled off at a peeling speed of 300 mm / min. In the present invention, adhesion between the glass plate and the adhesive layer The force a is measured by peeling the gas barrier laminate attached to the glass plate from the glass plate. Further, the adhesive force b between the gas barrier film and the protect film is measured by peeling the protect film from the gas barrier laminate attached to the glass plate.
In the present specification, the “gas barrier” means a function of preventing the permeation of a gas such as oxygen or water vapor.

The gas barrier laminated body of the present invention is not particularly limited as long as it has a laminated structure in which an adhesive layer, a gas barrier film, and a protective film are laminated in this order.
The layer structure of the gas barrier laminate of one aspect of the present invention includes, for example, the following aspects in which only the adhesive layer, the gas barrier film, and the protective film are laminated in this order, and further, optionally laminated on the adhesive layer. The following aspects having a release sheet to be formed can be mentioned.
-Adhesive layer / Gas barrier film / Protect film-Release sheet / Adhesive layer / Gas barrier film / Protect film The aspect of the layer structure having the release sheet represents the state before using the gas barrier laminate as a sealing material. It was done. When used as a sealing material, the release sheet is peeled off and removed, and the surface of the exposed adhesive layer and the object to be sealed are bonded to cover the object to be sealed and sealed. Then, the removal of the protective film laminated on the gas barrier film is performed in the process of sealing the object to be sealed with the gas barrier laminate to prepare the sealed body, or in the process of processing or transporting the sealed body. Will be done.

Further, the layer structure of the gas barrier laminate of the present invention is, for example, the following aspect after the surface of the exposed adhesive layer and the object to be sealed are bonded to cover the object to be sealed.
-Adhesive layer / Gas barrier film / Protect film Here, the adhesive layer contained in the gas barrier laminate of one aspect of the present invention may be a curable adhesive layer. In this case, after the curable adhesive layer is cured, the layer structure of the gas barrier laminate has the following aspects.
-Cured adhesive layer / gas barrier film / protective film In the present invention, the "curable adhesive layer" means an uncured adhesive layer.
In the sealed body produced by sealing the object to be sealed with the gas barrier laminate of the present invention, the gas barrier film is protected by the protective film until the protective film is peeled off, and the gas barrier film is scratched or cracked. Is prevented.
Here, after the protective film is peeled off from the sealing body, the mode is as follows.
-Adhesive layer / gas barrier film If the adhesive layer is a curable adhesive layer, after the curable adhesive layer is cured and the protective film is peeled off from the sealant, the following It becomes an aspect.
-Cured adhesive layer / gas barrier film In this specification, the surface of the exposed adhesive layer and the object to be sealed are bonded to cover the object to be sealed to seal the object to be sealed. Is referred to as a "sealing body". The adhesive layer may be uncured, cured, or intermediate between uncured and cured, that is, a semi-cured state.
When the adhesive layer of the sealing body is uncured or semi-cured, the sealing body can be said to be a “sealing precursor”.
Further, in the present invention, the process of processing the encapsulant includes a process of curing the adhesive layer of the encapsulant.

The present inventors have a process of storing and transporting the gas barrier laminate until it is used, a process of sealing the object to be sealed with the gas barrier laminate to prepare a sealed body, and the process of producing the sealed body. In order to prevent the gas barrier film from being scratched or cracked in the process of processing and transportation, it was considered to protect the entire surface of the gas barrier film with a protective film and peel off the protective film at a desired timing.
However, when the protective film is peeled off after sealing the object to be sealed with the gas barrier laminate, a gap is generated between the object to be sealed and the adhesive layer, and oxygen, water vapor, etc. infiltrate through the gap. It has become clear that the material to be sealed may deteriorate. It was also revealed that the appearance was poor.
In order to investigate the cause of this, the present inventors have conducted diligent studies. As a result, it was found that a gap is generated between the object to be sealed and the adhesive layer due to the force applied when the protective film is peeled off.
Therefore, in order to solve the above problem, the present inventors have conducted further diligent studies. As a result, when the gas barrier laminate is attached to the glass plate under specific conditions, the adhesive strength a between the glass plate and the adhesive layer and the adhesive strength b between the gas barrier film and the protective film are reduced. It has been found that the above problem can be solved by adjusting so as to satisfy the above equation (1).

From this, the present inventors protect at any timing of the process of sealing the object to be sealed with the gas barrier laminate to prepare the sealed body and the process of processing and transporting the sealed body. It has been found that even if the film is peeled off, no gap is generated between the object to be sealed and the adhesive layer, and a gas barrier laminate that is extremely easy to use in various processes can be provided, and the present invention has been completed. rice field.

[Physical characteristics of gas barrier laminate]
In the gas barrier laminate of the present invention, the gas barrier laminate is pressed against a glass plate with a roller under the following condition (α) with the adhesive layer as a bonding surface, and the gas barrier laminate and the glass plate are attached. After that, the film is peeled off under the following condition (β), and the other conditions are the adhesive strength a between the glass plate and the adhesive layer, and the gas barrier film and the protective film, which are measured in accordance with JIS Z0237: 2000. The adhesive force b between them is adjusted so as to satisfy the following formula (1).
a> b ... (1)
Condition (α): temperature 23 ° C., pressure 0.2 MPa, and speed 0.2 m / min
Condition (β): After application, leave to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then peel off at a peeling speed of 300 mm / min.

In the gas barrier laminate of the present invention, the adhesive force a between the glass plate and the adhesive layer is larger than the adhesive force b between the gas barrier film and the protective film, preferably 1.0 N / 50 mm or more, and more. It is preferably 2.0 N / 50 mm or more, more preferably 3 N / 50 mm or more, still more preferably 4 N / 50 mm or more, and even more preferably 5 N / 50 mm or more.
In the gas barrier laminate of one aspect of the present invention, the upper limit of the adhesive force a between the glass plate and the adhesive layer is not particularly limited, but is usually 20 N / 50 mm.

In the gas barrier laminate of the present invention, the adhesive force b between the gas barrier film and the protective film is smaller than the adhesive force a between the glass plate and the adhesive layer, preferably 1N / 50 mm or less, more preferably. It is 0.5 N / 50 mm or more, more preferably 0.4 N / 50 mm or less, and even more preferably 0.3 N / 50 mm or less.
In the gas barrier laminate of one aspect of the present invention, the lower limit of the adhesive force b between the gas barrier film and the protective film is not particularly limited, but is usually 0.05 N / 50 mm.

Further, in the gas barrier laminate according to one aspect of the present invention, the difference (ab) between the adhesive force a between the glass plate and the adhesive layer and the adhesive force b between the gas barrier film and the protective film is It is preferably 0.1 N / 50 mm or more, more preferably 0.3 N / 50 mm or more, and further preferably 0.7 N / 50 mm or more.

Hereinafter, regarding the adhesive layer, the gas barrier film, and the protective film constituting the laminated structure of the gas barrier laminate of the present invention, the adhesive force a between the glass plate and the adhesive layer and the space between the gas barrier film and the protective film A specific method for satisfying the above equation (1) regarding the adhesive strength b of the above will be described in detail.

[Adhesive layer]
The gas barrier laminate of the present invention has an adhesive layer.
The adhesive composition constituting the adhesive layer is not particularly limited as long as the above formula (1) is satisfied, and for example, a dry-solidified type adhesive composition, a heat-melt type adhesive composition, and a curable adhesive are used. An agent composition, a pressure-sensitive adhesive composition, and the like can be used. Specific examples of the adhesive composition constituting the adhesive layer include an adhesive composition containing an acrylic resin, an adhesive composition containing a urethane resin, and an adhesive composition containing a silicone resin. Examples thereof include a rubber-based adhesive composition, an adhesive composition containing a polyolefin-based resin, and an adhesive composition containing an epoxy-based resin.
These can be used alone or in combination of two or more.
The adhesive composition may contain a binder resin other than the above resin. Further, the adhesive composition may contain one or more selected from a curable component, a silane coupling agent, a catalyst, a polymerization initiator, a tackifier and the like. The thickness of the adhesive layer is preferably 0.5 to 300 μm, more preferably 3 to 200 μm, still more preferably 5 to 150 μm, still more preferably, from the viewpoint of ensuring excellent sealing performance against the object to be sealed. Is 5 to 80 μm.

The water vapor permeability of the adhesive layer is preferably 100 g / m ² · day or less, more preferably 85 g / m ² · day or less, ^{still more preferably 70 g / m 2} ·, from the viewpoint of ensuring good gas barrier properties. It is less than or equal to day.
In the present specification, the "water vapor permeability of the adhesive layer" means a value measured using a gas permeability measuring device (manufactured by mocon, product name "PERMATRAN"), but is used for other general purposes. The measured value using the water vapor transmission rate measuring device shows the same value.

Here, the adhesive layer contained in the gas barrier laminate of one aspect of the present invention is preferably a curable adhesive layer. Since the adhesive layer is curable, the adhesive layer is in an uncured state at the time of sticking, so that it can be easily stuck to the object to be sealed and has good followability to the unevenness of the object to be sealed. Can be. Then, the curable adhesive layer is attached to the object to be sealed and then cured, so that the object to be sealed and the adhesive layer are firmly adhered to each other. As a result, the gas barrier laminate is excellent in the ability to prevent deterioration of the sealed object due to the infiltration of oxygen, water vapor and the like.
The water vapor permeability of the curable adhesive layer is preferably in the same range as the above-mentioned "water vapor permeability of the adhesive layer" from the viewpoint of ensuring good gas barrier properties. The "water vapor permeability of the curable adhesive layer" can be measured by the same measuring method as the above-mentioned "water vapor permeability of the adhesive layer".
The curable adhesive layer is a curable adhesive composition, specifically, for example, a thermosetting adhesive composition or an energy ray-curable adhesive composition that can be cured by heat or energy rays. Formed from.
The energy ray means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, electron beams, and the like, and ultraviolet rays are preferable.
The curable adhesive layer is preferably a thermosetting adhesive layer formed from a thermosetting adhesive composition.

Here, in one aspect of the present invention, the curable adhesive layer is formed by an adhesive composition containing a curable component (B). Further, from the viewpoint of further improving the sealing performance, it is more preferable that the curable adhesive layer is formed of an adhesive composition containing both the polyolefin resin (A) and the curable component (B).

Further, in one aspect of the present invention, the adhesive composition for forming the curable adhesive layer may contain components other than the polyolefin resin (A) and the curable component (B). .. Examples of the other components include a binder resin (A') other than the polyolefin resin (A), a silane coupling agent (C), a curing catalyst (D), a cationic polymerization initiator (D'), and a tackifier (tightening agent). One or more selected from E) can be mentioned.
In the following description, "polyolefin resin (A)", "binder resin other than polyolefin resin (A')", "curable component (B)", "silane coupling agent (C)", ""Curing catalyst (D)", "cationic polymerization initiator (D')", and "adhesive-imparting agent (E)" are "component (A)", "component (A')", and "component (B)", respectively. , "Component (C)", "Component (D)", "Component (D')", and "Component (E)".

In one aspect of the present invention, the total content of the components (A) and (B) in the adhesive composition containing both the polyolefin resin (A) and the curable component (B) is the adhesive composition. With respect to the total amount (100% by mass) of the active ingredient, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99. It is mass% or more, and is usually 100 mass% or less.
Further, the adhesive composition is selected from the components (A'), (C), (D), (D'), and (E) in addition to the polyolefin resin (A) and the curable component (B). When containing one or more of the components (A) and (B) in the adhesive composition, select from the components (A'), (C), (D), (D'), and (E). The total content of the adhesive composition with one or more components is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, based on the total amount (100% by mass) of the active ingredient of the adhesive composition. It is more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.
In the present specification, the "active ingredient of the adhesive composition" means a component (solid content) excluding the diluting solvent contained in the adhesive composition.

Hereinafter, the components (A), (B), (A'), (C), (D), (D'), and (E) in the adhesive composition will be described in detail.

<Polyolefin resin (A)>
In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a polyolefin resin (A).
As used herein, the term "polyolefin-based resin" means a polymer having a repeating unit derived from an olefin-based monomer.
Since the adhesive composition contains the polyolefin resin (A), the water vapor permeability of the adhesive layer after curing tends to be lowered. Therefore, it is easy to improve the water vapor blocking property of the adhesive layer after curing.
The content of the polyolefin resin (A) in the adhesive composition is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, based on the total amount (100% by mass) of the active ingredients of the adhesive composition. %, More preferably 50 to 80% by mass.
When the content of the polyolefin resin (A) is in the above range, the water vapor transmittance of the adhesive layer after curing is more likely to be lowered.
As the content of the polyolefin resin (A) in the adhesive composition increases, the adhesive strength a between the glass plate and the curable adhesive layer tends to decrease, but the gas barrier film and the protector tend to decrease. The above formula (1) can be satisfied by adjusting the adhesive force b between the film and the film to a value lower than the adhesive force a. Further, the content of the polyolefin resin (A) in the adhesive composition is reduced within a range that satisfies the required water vapor blocking property, and the adhesive force a between the glass plate and the curable adhesive layer is adhered. The above equation (1) can be satisfied by adjusting the force to a value higher than b.

The olefin-based monomer contained in the polyolefin-based resin (A) is preferably an α-olefin having 2 to 8 carbon atoms, and among them, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-1-. Penten and 1-hexene are preferred.
The polyolefin resin (A) may have two or more types of α-olefin-derived units. Further, the polyolefin-based resin (A) may be a polymer consisting of only repeating units derived from an olefin-based monomer, or may be copolymerized with a repeating unit derived from an olefin-based monomer and an olefin-based monomer. It may be a copolymer composed of a repeating unit derived from a possible monomer. Examples of the monomer copolymerizable with the olefin-based monomer include vinyl acetate, (meth) acrylic acid ester, and styrene.
In addition, in this specification, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms.

Specific examples of the polyolefin resin (A) include ultra-low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, and 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 , Polyisobutylene, polyisoprene and the like.
These may be used alone or in combination of two or more.

Here, in one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the polyolefin resin (A) is modified from the viewpoint of further improving the sealing performance of the adhesive layer after curing. It is preferable to contain a polyolefin resin (A1).
In the present specification, the "modified polyolefin resin (A1)" means that the precursor polyolefin resin (A) reacts with the modifier, and the functionality of the modifier on the main chain polyolefin resin (A). It means a polymer in which a group is introduced as a side chain.
The modifier may have two or more functional groups in the molecule.

Examples of the functional group contained in the modifier and which can be introduced as a side chain into the polyolefin resin (A) serving as the main chain include a carboxyl group, a group derived from a carboxylic acid anhydride, and a carboxylic acid. Ester group, hydroxyl group, epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphon group, nitro group, urethane group, Halogen atoms, alkoxysilyls and the like can be mentioned.
Among these functional groups, 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, an isocyanate and an alkoxysilyl group are preferable, and among them, the carboxylic acid anhydride is used. Derived groups are preferred.

Here, the modified polyolefin resin (A1) is preferably an acid-modified polyolefin resin from the viewpoint of enhancing the reactivity with the curable component (B).
In the present specification, the "acid-modified polyolefin-based resin" means that the polyolefin-based resin (A) as a precursor reacts with a compound having an acid group, and the acid group is on the side of the polyolefin-based resin (A) as a main chain. It means a polymer introduced as a chain.
The method and conditions for introducing the acid group of the compound having an acid group into the polyolefin resin (A) as the main chain as a side chain are not particularly limited, and a known side chain introduction method may be adopted. can.

The compound having an acid group is not particularly limited as long as it can be introduced as a side chain into the polyolefin resin (A) as the main chain, but unsaturated carboxylic acid and its anhydride are preferable. ..
Examples of unsaturated carboxylic acids and their anhydrides include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, and citraconic anhydride. , Aconitic anhydride, norbornendicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like.
These unsaturated carboxylic acids and their anhydrides can be used alone or in combination of two or more.
Among these unsaturated carboxylic acids and their anhydrides, maleic anhydride is preferable from the viewpoint of further improving the sealing performance of the adhesive layer after curing.

The acid-modified polyolefin resin may be a commercially available product.
Examples of commercially available acid-modified polyolefin resins include Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistor (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), and orevac (registered trademark). (Arkema), Modic (registered trademark) (Mitsubishi Chemical) and the like can be mentioned.

The blending amount of the compound having an acid group to react with the polyolefin resin (A) as a precursor is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin (A) as a precursor. , More preferably 0.2 to 3 parts by mass, still more preferably 0.2 to 1.0 parts by mass.
When the blending amount of the compound having an acid group is within the above range, it is easy to improve the sealing performance of the adhesive layer after curing.

The weight average molecular weight (Mw) of the polyolefin-based resin (A) and the modified polyolefin-based resin (A1) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and even more preferably. Is 25,000 to 250,000, more preferably 30,000 to 150,000.
When the weight average molecular weight (Mw) of the polyolefin-based resin (A) and the modified polyolefin-based resin (A1) is in the above range, the adhesive layer formed from the adhesive composition can be easily maintained in a sheet shape.

In one aspect of the present invention, the polyolefin-based resin (A) may be composed of only the modified polyolefin-based resin (A1), or may be composed of the modified polyolefin-based resin (A1) and the non-modified polyolefin-based resin. May be done.
The content of the modified polyolefin resin (A1) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80, based on the total amount (100% by mass) of the polyolefin resin (A). It is ~ 100% by mass, more preferably 90 to 100% by mass.
When the content of the modified polyolefin resin (A1) is within the above range, it is easy to further improve the sealing performance of the adhesive layer after curing.

<Curable component (B)>
In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition contains a curable component (B).
In the present specification, the “curable component (B)” means a component that becomes a network structure and is cured in an insoluble and insoluble state by heating or irradiation with energy rays.
When the adhesive composition contains the curable component (B), the adhesive layer becomes curable, and the sealing performance of the adhesive layer after curing is improved.
The curable component (B) may be a thermosetting component or an energy ray-curable component, but is preferably a thermosetting component.
The content of the curable component (B) in the adhesive composition is preferably 5 to 50% by mass, more preferably 5 to 48% by mass, based on the total amount (100% by mass) of the active ingredient of the adhesive composition. %, More preferably 5 to 45% by mass, still more preferably 10 to 40% by mass.
When the content of the curable component (B) is within the above range, it is easy to further improve the sealing performance of the adhesive layer after curing.
When the adhesive composition contains the polyolefin resin (A), the content of the curable component (B) with respect to 100 parts by mass of the polyolefin resin (A) in the adhesive composition is preferably 5 to 110. It is by mass, more preferably 10 to 100 parts by mass. When the adhesive layer formed from the adhesive composition having the content of the curable component (B) within this range is cured, the cured adhesive layer is more excellent in water vapor blocking property.

Examples of the curable component (B) include curable epoxy resin, melamine resin, urea resin, maleimide resin and the like. These can be used alone or in combination of two or more. Among these, it is preferable to include a curable epoxy resin (B1).
In the present specification, the "curable epoxy resin (B1)" means an epoxy compound that has a network structure and is cured in an insoluble and insoluble state by heating or irradiation with energy rays.

Further, the curable epoxy resin (B1) preferably contains a polyfunctional epoxy resin (B2).
As used herein, the term "polyfunctional epoxy resin (B2)" means a compound having at least two or more epoxy groups in the molecule.

As the polyfunctional epoxy resin (B2), a bifunctional epoxy resin having two epoxy groups in the molecule is preferable from the viewpoint of further improving the sealing performance of the adhesive layer after curing.
Examples of the bifunctional epoxy resin include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether. , Aromatic epoxy compounds such as novolak type epoxy resin (for example, phenol / novolak type epoxy resin, cresol / novolak type epoxy resin, brominated phenol / novolak type epoxy resin); hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F di Alicyclic epoxy compounds such as glycidyl ether and hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, tri Examples thereof include aliphatic epoxy compounds such as methylol propane polyglycidyl ether, 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane, and dimethylol tricyclodecane diglycidyl ether. These bifunctional epoxy resins may be used alone or in combination of two or more.

Here, in one aspect of the present invention, the adhesive composition preferably contains a polyfunctional epoxy compound (BL) which is a liquid at 25 ° C. as a component (B).
In the following description, the polyfunctional epoxy compound (BL) which is liquid at 25 ° C. is also referred to as “component (BL)”.
The component (BL) has an effect of lowering the storage elastic modulus of the adhesive composition when the temperature of the adhesive composition becomes high (hereinafter, also referred to as “storage elastic modulus lowering effect”). Therefore, in one aspect of the present invention, when the adhesive composition contains such a component (BL), an adhesive layer having excellent unevenness followability can be efficiently formed.

The weight average molecular weight (Mw) of the component (BL) is preferably 1,000 or more, more preferably 1,200 or more, still more preferably 1, from the viewpoint of suppressing the generation of outgas caused by the component (BL). It is 500 or more, more preferably 1,800 or more, and even more preferably 2,100 or more.
Further, from the viewpoint of obtaining an adhesive composition having a further improved storage elastic modulus lowering effect, the weight average molecular weight (Mw) of the component (BL) is preferably 5,000 or less, more preferably 4,500 or less.
The adhesive force a between the glass plate and the curable adhesive layer changes depending on the size of the weight average molecular weight (Mw) of the component (BL). Specifically, the larger the weight average molecular weight (Mw) of the component (BL) in the adhesive composition, the lower the adhesive force a tends to be, but the adhesive force b between the gas barrier film and the protective film tends to decrease. The above formula (1) can be satisfied by adjusting the adhesive strength to a value lower than a. Further, the weight average molecular weight (Mw) of the component (BL) is reduced within the range satisfying the required outgas generation suppression performance, and the adhesive force a between the glass plate and the curable adhesive layer is made larger than the adhesive force b. The above equation (1) can be satisfied by adjusting to a high value.

The epoxy equivalent of the component (BL) is preferably 100 to 1,500 g / eq, more preferably 150 to 1500 g / eq, even more preferably 200 to 1,400 g / eq, even more preferably 240 to 1,300 g / eq. Is.
As used herein, the term "epoxy equivalent" means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and is a value measured in accordance with JIS K 7236: 2009.

The content of the component (BL) in the adhesive composition is preferably 5 to 40% by mass, more preferably 8 to 36% by mass, based on the total amount (100% by mass) of the active ingredients of the adhesive composition. More preferably, it is 10 to 34% by mass.
When the content of the component (BL) is within this range, the effect of lowering the storage elastic modulus is obtained, and the generation of outgas caused by the component (BL) is also suppressed. The adhesive force a between the glass plate and the curable adhesive layer changes as the content of the component (BL) increases or decreases. When the content of the component (BL) in the adhesive composition is small, the adhesive strength a tends to decrease. In this case, the above formula (1) can be satisfied by adjusting the adhesive force b between the gas barrier film and the protective film to a value lower than the adhesive force a. Further, by increasing the content of the component (BL) in the adhesive composition and adjusting the adhesive force a between the glass plate and the curable adhesive layer to a value higher than the adhesive force b, the above-mentioned Equation (1) can be satisfied.

<Binder resin (A') other than polyolefin resin (A)>
In one aspect of the present invention, the adhesive composition may contain a binder resin (A') other than the polyolefin resin (A). Examples of the binder resin (A') other than the polyolefin-based resin include phenoxy-based resin and acetal-based resin.
The binder resin (A') other than the polyolefin-based resin (A) may be used together with the polyolefin-based resin (A) or may be used in place of the polyolefin-based resin (A).

<Silane coupling agent (C)>
In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a silane coupling agent (C).
As used herein, the term "silane coupling agent (C)" means an organosilicon compound having two or more different reactive groups in the molecule.
Since the adhesive composition further contains the silane coupling agent (C), it is easy to ensure good sealing performance of the adhesive layer after curing in both normal temperature and high temperature environments. Even when the adhesive layer is not curable, the adhesive composition may contain a silane coupling agent (C). In this case as well, it is easy to ensure good sealing performance of the adhesive layer.
The content of the silane coupling agent in the adhesive composition is preferably 0.01 to 0.1% by mass, more preferably 0.02 to 0%, based on the total amount (100% by mass) of the adhesive composition. It is 09% by mass.
When the adhesive composition contains the polyolefin resin (A), the content of the silane coupling agent (C) in the adhesive composition is preferably based on 100 parts by mass of the polyolefin resin (A). It is 0.01 to 5.0 parts by mass, more preferably 0.05 to 1.0 parts by mass.
When the content of the silane coupling agent (C) is within the above range, it is easy to ensure good sealing performance of the adhesive layer after curing even when exposed for a long time in a high temperature and high humidity environment. ..

The silane coupling agent (C) has at least one alkoxysilyl group in the molecule from the viewpoint of facilitating better sealing performance of the adhesive layer after curing in both normal temperature and high temperature environments. An organosilicon compound having is preferable.
Examples of such a silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacrypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2 -Silicon compounds having an epoxy structure such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane; 3-aminopropyltrimethoxysilane, Amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3 -Isocyanopropyltriethoxysilane; etc. These silane coupling agents may be used alone or in combination of two or more.

<Curing catalyst (D)>
In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a curing catalyst (D).
As used herein, the term "curing catalyst (D)" means a catalyst that promotes a reaction in which a curable component (B) is cured by heat or energy rays.
Since the adhesive composition contains the curing catalyst (D), it is easy to improve the sealing performance of the adhesive layer after curing at a high temperature.
The content of the curing catalyst (D) contained in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the curable component (B). Is.
When the content of the curing catalyst (D) is within the above range, it is easy to further improve the sealing performance of the adhesive layer after curing at a high temperature.

As the curing catalyst (D), when the curable component (B) is a thermosetting component, an imidazole-based curing catalyst, which is a thermosetting type curing catalyst, is preferable from the viewpoint of preferably advancing curing by heating.
Examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2 Examples thereof include −phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole. These imidazole-based curing catalysts can be used alone or in combination of two or more.
Among these imidazole-based curing catalysts, 2-ethyl-4-methylimidazole is preferable.

<Cationic polymerization initiator (D')>
In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition also preferably contains a cationic polymerization initiator (D'). When the adhesive layer is a thermosetting adhesive layer, the cationic polymerization initiator (D') is preferably a thermocation polymerization initiator, and the adhesive layer is an energy ray-curable adhesive layer. If this is the case, it is preferably a photocationic polymerization initiator. Examples of the thermal cationic polymerization initiator include sulfonium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, iodonium salts and the like, and sulfonium salts are preferable. Examples of the photocationic polymerization initiator include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, ammonium salt compounds, antimonate compounds, diazonium salt compounds, selenium salt compounds, and oxonium salt compounds. , Bromine salt-based compounds and the like, and sulfonium salt-based compounds are preferable.
When the adhesive composition contains a cationic polymerization initiator (D'), the curable component (B) is preferably a curable epoxy resin (B1).

<Adhesive imparting agent (E)>
In one aspect of the present invention, the adhesive composition may contain a tackifier (E) when the adhesive layer is a curable adhesive layer.
The tackifier (E) used in one embodiment of the present invention is a component that supplementarily improves the tackiness of the curable adhesive layer, and is an oligomer having a weight average molecular weight (Mw) of usually less than 10,000. It refers to and is distinguished from the resin (X) contained in the pressure-sensitive adhesive composition described later. Even when the adhesive layer is not curable, the adhesive composition may contain the tackifier (E).
The weight average molecular weight (Mw) of the tackifier (E) is usually less than 10,000, but is preferably 400 to 8000, more preferably 500 to 5000, and even more preferably 800 to 3500.

The content of the tackifier (E) in the adhesive composition is preferably reduced from the viewpoint of suppressing the generation of outgas caused by the tackifier (E), and is the total amount of the active ingredients of the adhesive composition. With respect to (100% by mass), it is preferably more than 0% by mass and 30% by mass or less, more preferably more than 0% by mass and 15% by mass or less, and further preferably 1 to 10% by mass. Further, when it is desired to suppress the generation of outgas as much as possible, it is also preferable that the adhesive composition does not contain the tackifier (E).
The content of the tackifier (E) contained in the adhesive composition is preferably more than 0 parts by mass to 80 parts by mass, and more preferably 0 parts by mass with respect to 100 parts by mass of the polyolefin resin (A). Ultra to 30 parts by mass, more preferably 1 to 20 parts by mass. Further, when it is desired to suppress the generation of outgas as much as possible, the content of the tackifier (E) is preferably as small as possible with respect to 100 parts by mass of the polyolefin resin (A), and is 0 parts by mass. Is more preferable.
On the other hand, if the content of the tackifier (E) in the adhesive composition is small, the adhesive force a between the glass plate and the curable adhesive layer tends to decrease. In this case, the above formula (1) can be satisfied by adjusting the adhesive force b between the gas barrier film and the protective film to a lower value. Further, by increasing the content of the pressure-sensitive adhesive (E) in the adhesive composition within a range that satisfies the required outgas generation suppression performance, the adhesive strength a between the glass plate and the curable adhesive layer can be increased. The above equation (1) can also be satisfied by adjusting the adhesive strength to a value higher than b.

Examples of the tackifier (E) include rosin-based resins such as polymerized rosin, polymerized rosin ester, and rosin derivative; Inden resin; aliphatic petroleum resin, aromatic petroleum resin and its hydride, aliphatic / aromatic copolymer petroleum resin and other petroleum resins; styrene or substituted styrene polymer; α-methylstyrene monopolymer resin , Polymers of α-methylstyrene and styrene, copolymers of styrene-based monomers and aliphatic monomers, copolymers of styrene-based monomers and α-methylstyrene and aliphatic monomers, from styrene-based monomers Such as a homopolymer, a styrene resin such as a copolymer of a styrene monomer and an aromatic monomer; and the like. These tackifiers (E) may be used alone or in combination of two or more.
Among these, as the tackifier (E), 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 (E) is a viewpoint of further improving the shape-retaining property of the formed adhesive layer and enabling the cured adhesive layer to exhibit excellent adhesiveness even in a high temperature environment. Therefore, it is preferably 80 ° C. or higher, more preferably 85 to 170 ° C., and even more preferably 90 to 150 ° C.
In this specification, the softening point means a value measured in accordance with JIS K 5902.
When two or more kinds of tackifiers (E) are used, it is preferable that the weighted average of the softening points of the plurality of tackifiers belongs to the above range.

<Other additives>
In one aspect of the present invention, the adhesive composition may contain other additives other than the above-mentioned components (A) to (E) as long as the effects of the present invention are not significantly impaired.
Other additives are appropriately selected depending on the intended use, and are, for example, ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, bulking agents, softeners and the like. Additives can be mentioned.
These additives may be used alone or in combination of two or more.
Even when the adhesive layer is not curable, the pressure-sensitive adhesive composition may contain these additives.

<Diluting solvent>
In one aspect of the present invention, the adhesive composition may further contain a diluting solvent from the viewpoint of improving the moldability of the adhesive layer.
The diluting solvent can be appropriately selected from organic solvents, and specifically, aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, and the like. Ketone solvents such as methylisobutylketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane; and the like. ..
These solvents may be used alone or in combination of two or more.
The content of the solvent is appropriately set in consideration of coatability and the like.
Further, even when the adhesive layer is not curable, the pressure-sensitive adhesive composition may contain a diluting solvent from the same viewpoint.

<Method of forming the adhesive layer>
The method for forming the adhesive layer constituting the gas barrier laminate of the present invention is not particularly limited, and it can be appropriately formed by adopting a known method or the like.
Here, in one aspect of the present invention, the adhesive layer is preferably formed from the above-mentioned adhesive composition. For example, a method of applying the above-mentioned adhesive composition on the peel-processed surface of the above-mentioned release sheet to form a coating film, and drying the coating film to form an adhesive layer can be mentioned.
In the present specification, when the adhesive layer is a curable adhesive layer, the heat treatment by heat applied when the coating film is dried in the process of forming the curable adhesive layer is curable. It is not included in the curing process of the adhesive layer.

Examples of the method for applying the adhesive composition include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.
Further, from the viewpoint of improving the coatability, it is preferable to add the above-mentioned diluting solvent to the adhesive composition to form a solution.
As the drying conditions for drying the coating film, for example, it is preferable to carry out a drying treatment at 80 to 130 ° C., preferably 90 to 110 ° C. for 30 seconds to 5 minutes.

[Gas barrier film]
The gas barrier laminate of the present invention has a gas barrier film. The gas barrier film is laminated on the adhesive layer. When the gas barrier laminate of the present invention has a gas barrier film, it is possible to exhibit excellent gas barrier properties that are highly effective in preventing the permeation of gases such as oxygen and water vapor.
Further, in the gas barrier laminate of the present invention, a protective film is laminated on the gas barrier film, and the gas barrier film is protected by the protective film. Therefore, in addition to the process of storing and transporting the gas barrier laminate until use, the process of sealing the object to be sealed with the gas barrier laminate to prepare a sealed body, processing and transport of the sealed body, etc. In the process, it is possible to prevent the gas barrier film from being scratched or cracked.

In one aspect of the present invention, the gas barrier film contained in the gas barrier laminate is preferably a film having at least a base material layer and having a gas barrier function. One aspect of the gas barrier film is one having a base material layer and a gas barrier layer. For example, an embodiment having the following layer structure can be mentioned.
-Base material layer / gas barrier layer Further, in the above-mentioned "base material layer / gas barrier layer" aspect, in order to improve the adhesion between the base material layer and the gas barrier layer, the base material layer and the gas barrier are as shown in the following aspects. An anchor coat layer may be provided between the layers.
・ Base material layer / anchor coat layer / gas barrier layer

In one aspect of the present invention, the gas barrier film contained in the gas barrier laminate is a single-layer resin film or the like in which the base material layer itself has a gas barrier function and the base material layer also has a function as a gas barrier layer. May be good.

In one aspect of the present invention, it is preferable that the gas barrier layer is arranged at a position closer to the adhesive layer than the base material layer, for example, as in the following aspect.
-Base material layer / gas barrier layer / adhesive layer As a result, the base material layer does not intervene between the gas barrier layer and the adhesive layer, so that the performance of the gas barrier laminate to block water vapor is further improved.
When the gas barrier layer is arranged at a position closer to the adhesive layer than the base material layer, the protect film is laminated on the base material layer of the gas barrier film. Since a resin film is used as the base material layer as described later, the adhesiveness between the protect film and the base material layer tends to increase. Further, even when the protect film is not directly laminated on the base material layer, if the protect film is laminated via some organic layer provided on the base material layer, the adhesiveness between the protect film and the base material layer is obtained. Is easy to increase. However, since the gas barrier laminate of the present invention is adjusted so as to satisfy the relationship of the above formula (1), there is a gap between the object to be sealed and the adhesive layer when the protective film is peeled off. Does not occur.

In one aspect of the present invention, the water vapor permeability of the gas barrier film of the gas barrier laminate in an environment of a temperature of 40 ° C. and 90% RH (relative humidity) is preferably 0.1 g / m ² / day or less. more preferably 0.05g ^/ m 2 ^/ day, more preferably not more than 0.005g ^/ m 2 ^/ day.
Since the water vapor permeability of the gas barrier film is 0.1 g / m ² / day or less, it is easy to effectively suppress the deterioration of the object to be sealed by using the gas barrier laminate. For example, it is easy to suppress the infiltration of oxygen, water vapor, etc. into the inside of an element such as an organic EL element formed on a transparent substrate, and effectively suppress the deterioration of the electrode and the organic layer.
Further, also for the gas barrier laminate having the gas barrier film and the adhesive layer, the water vapor transmittance in an environment of a temperature of 40 ° C. and 90% RH (relative humidity) is preferably the same value as described above.
In the present specification, the "water vapor transmission rate of the gas barrier film" means a value measured using a gas transmission rate measuring device (manufactured by mocon, product name "AQUATRAN 2"), but is used for other general purposes. The measured value using the water vapor transmission rate measuring device shows the same value.

In one aspect of the present invention, the gas barrier film contained in the gas barrier laminate preferably has optical transparency. Specifically, the total light transmittance measured in accordance with JIS K7136: 2000 is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. .. ^{Further, the b * value in the L *} a ^* b ^* display color system measured in accordance with JIS K7136: 2000 is preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less. Is.

Hereinafter, as the gas barrier film used for the gas barrier laminated body of one aspect of the present invention, a gas barrier film having a laminated structure in which a base material layer and a gas barrier layer are laminated will be described in detail as an example.

<Base material layer>
As the base material layer of the gas barrier film, a resin film containing a resin component is preferable.
The resin components include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, and cycloolefin type. Examples thereof include polymers, cycloolefin-based copolymers, aromatic polymers, and polyurethane-based polymers.
Among these, polycarbonate, cycloolefin-based polymer, and cycloolefin-based copolymer are preferable from the viewpoint of forming a gas barrier film having high transparency and optically isotropic property.
In addition, these resins can be used individually by 1 type or in combination of 2 or more types. Further, the base material layer may be a laminate of two or more types of resin films.
A resin film having optical isotropic properties is a more preferable resin film as a constituent material of a gas barrier film when a light emitting element such as an organic EL element is used for a display application, but it is inferior in flexibility and brittle, so that it may be scratched during handling. It has the drawback of being prone to cracking.
In the gas barrier laminate of the present invention, even when a brittle resin film having inferior flexibility such as polycarbonate, cycloolefin polymer, cycloolefin copolymer and the like is used as a constituent material of the gas barrier film, the gas barrier film is used. Is protected by the protective film, it is possible to prevent the gas barrier film from being scratched or cracked during handling, and it is possible to prevent defects such as bright spots caused by the scratches or cracks from occurring on the display. Therefore, the yield can be improved in a display manufacturing process or the like using a light emitting element such as an organic EL element.

The thickness of the base material layer of the gas barrier film is not particularly limited, and is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and further preferably 5 to 100 μm.
Here, in the gas barrier laminate of the present invention, a protective film is laminated on the gas barrier film. Therefore, even when the base material layer is thin, the thickness of the gas barrier laminate can be ensured by the protect film, so that the handleability of the gas barrier laminate can be sufficiently ensured. Therefore, the thickness of the base material layer may be 30 μm or less, which makes it difficult to secure handleability in general. Therefore, the thickness of the base material layer contained in the gas barrier laminate of one aspect of the present invention may be 1 to 30 μm, 1 to 25 μm, or 1 to 20 μm.

<Gas barrier layer>
The gas barrier layer of the gas barrier film contains an inorganic film and a polymer compound from the viewpoint of being able to reduce the thickness of the gas barrier film and having excellent gas barrier properties, and is a modified polymer. The layer is preferable, and the polymer layer is more preferable. Since the polymer layer is a gas barrier layer, the gas barrier layer can be made highly flexible, and the durability of the gas barrier film against bending can be made excellent.

Examples of the polymer compound contained in the polymer layer include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, and the like. Examples thereof include polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer and the like.
These polymer compounds may be used alone or in combination of two or more.
Among these, from the viewpoint of being able to form a gas barrier layer having excellent gas barrier properties, the polymer compound contained in the polymer layer is preferably a silicon-containing polymer compound, and more preferably a polysilazane-based compound.
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 a -Si-N- bond (silazane bond) in the molecule, and specifically, a polymer having a repeating unit represented by the following general formula (I). Is preferable.

In the above general formula (I), n represents the number of repeating units and represents an integer of 1 or more.
Rx, Ry, and Rz are independently hydrogen atoms, alkyl groups having unsubstituted or substituents, cycloalkyl groups having unsubstituted or substituents, alkenyl groups having unsubstituted or substituents, unsubstituted or substituted, respectively. 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 Rx, Ry, and Rz in the general formula (I) are all 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 compound may be used alone or in combination of two or more.
Further, as the polysilazane-based compound, a modified polysilazane can be used, or a commercially available product can also be used.

In addition to the above-mentioned polymer compound, the polymer layer may further contain other components as long as the effects of the present invention are not impaired.
Examples of other components include curing agents, other polymers, antiaging agents, light stabilizers, flame retardants and the like.
These can be used alone or in combination of two or more.
The content of the polymer compound in the polymer layer is preferably 50 to 100 with respect to the total amount (100% by mass) of the components in the polymer layer from the viewpoint of forming a gas barrier layer having more excellent gas barrier properties. It is by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

The thickness of the polymer layer of the gas barrier film is preferably 50 to 500 nm, more preferably 50 to 300 nm, and even more preferably 50 to 200 nm.
In the present invention, even if the thickness of the polymer layer is on the nano-order, a gas-barrier laminate having sufficient gas-barrier properties can be obtained.

As a method for forming the polymer layer, for example, a solution for forming a polymer layer containing at least one kind of polymer compound, optionally other components, a solvent and the like can be used as a spin coater, a knife coater, a gravure coater or the like. Examples thereof include a method of forming a coating film by coating using a known device and drying the coating film to form the coating film.

Examples of the modification treatment of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment and the like. These processes may be performed individually by one type, or may be performed by combining two or more types.
The ion implantation treatment is a method of modifying the polymer layer by injecting ions into the polymer layer, as will be described later.
Plasma treatment is a method of modifying a polymer layer by exposing the polymer layer to plasma. For example, plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
The ultraviolet irradiation treatment is a method of irradiating the polymer layer with ultraviolet rays to modify the polymer layer. For example, the ultraviolet modification treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2013-226757.
Among these, ion implantation is used as a modification treatment for the polymer layer from the viewpoint that it is possible to efficiently modify the inside of the polymer layer without roughening the surface and form a gas barrier layer having more excellent gas barrier properties. Treatment is preferred.

Examples of the ions injected into the polymer layer during the ion injection process include ions of rare gases such as argon, helium, neon, krypton, and xenone; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, and fluorine. , Sulfur and other ions; Alkane-based gas ions such as methane and ethane; Alken-based gas ions such as ethylene and propylene; Alkane-based gas ions such as pentadiene and butadiene; Alkyne-based gas ions such as acetylene Ions; 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 organic silicon compounds; etc. Can be mentioned.
These ions may be used alone or in combination of two or more.
Among these, noble gas ions such as argon, helium, neon, krypton, and xenon are preferable from the viewpoint that ions can be injected more easily and a gas barrier layer having particularly excellent gas barrier properties can be obtained. Argon ions are more preferred.

The method of injecting ions is not particularly limited. For example, a method of irradiating ions (ion beams) accelerated by an electric field, a method of injecting ions in plasma (ions of plasma-producing gas), and the like can be mentioned, and a gas barrier layer can be easily obtained. The method of injecting ions is preferable.
In the method of injecting ions in plasma, for example, plasma is generated in an atmosphere containing a plasma-generating gas, and a negative high-voltage pulse is applied to the layer into which the ions are injected, so that the ions (cations) in the plasma are injected. Can be injected into the surface of the layer into which the ions are injected.

Examples of the inorganic film used as the gas barrier layer include a film formed by vapor deposition of an inorganic compound or metal. As raw materials for the film of the inorganic compound, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride and titanium nitride; inorganic carbides; inorganic Examples thereof include sulfides; inorganic oxide nitrides such as silicon oxide nitride; inorganic oxide carbides; inorganic carbide carbides; and inorganic carbide carbides.
Examples of the raw material of the metal film include aluminum, magnesium, zinc, tin and the like.
These can be used alone or in combination of two or more.
Among these, an inorganic film made of an inorganic oxide, an inorganic nitride or a metal is preferable from the viewpoint of gas barrier property, and further, an inorganic film made of an inorganic oxide or an inorganic nitride as a raw material is preferable from the viewpoint of transparency. Is preferable. Further, the inorganic film may be a single layer or a multilayer.

The thickness of the inorganic film is preferably in the range of 10 to 2000 nm, more preferably 20 to 1000 nm, more preferably 30 to 500 nm, and further preferably 40 to 200 nm from the viewpoint of gas barrier properties and handleability.

Examples of the vapor deposition method for forming an inorganic film include PVD (physical vapor deposition) methods such as vacuum vapor deposition, sputtering, and ion plating, and CVD such as thermal CVD, plasma CVD, and optical CVD. The method (chemical vapor deposition method) can be mentioned.

<Anchor coat layer>
In one aspect of the present invention, an anchor coat layer may be provided between the base material layer and the gas barrier layer from the viewpoint of further improving the adhesion between the base material layer and the gas barrier layer.
Examples of the anchor coat layer include a layer obtained by curing a composition containing an ultraviolet curable compound. The composition containing the ultraviolet curable compound may contain an inorganic filler such as silica particles.
The thickness of the anchor coat layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[Protect film]
The gas barrier laminate of the present invention has a protective film. The protective film is laminated on the gas barrier film to protect the gas barrier film.
Further, even if the protective film is peeled off at a desired timing such as when the protection of the gas barrier film becomes unnecessary or when it becomes necessary to expose the gas barrier film, there is a gap between the object to be sealed and the adhesive layer. Is not generated, and the infiltration of oxygen, water, etc. is prevented. In addition, it is possible to prevent the appearance from being poor.

In one aspect of the present invention, the protective film contained in the gas barrier laminate has at least a protective layer. The protective film may be a single layer of the protective layer, but a laminated structure of the protective layer and the pressure-sensitive adhesive layer is preferable. By forming a laminated structure of the protective layer and the adhesive layer, it is easy to adjust the adhesive force of the protective film to obtain a gas barrier laminated body satisfying the above formula (1).

By having the protective film, the gas barrier laminate of the present invention can improve the handleability of the gas barrier laminate while thinning the base material layer of the gas barrier film.
In one aspect of the present invention, the total thickness of the base film layer of the protective film and the gas barrier film is preferably 40 to 500 μm, more preferably 40 to 200 μm, and further preferably 50 to 150 μm.

Hereinafter, as the protective film used for the gas barrier laminated body of one aspect of the present invention, a protective film having a laminated structure in which a protective layer and an adhesive layer are laminated will be described in detail as an example.

<Protect layer>
As the protective layer of the protective film, a resin film containing a resin component is preferable.
Examples of the resin component include those having high impact resistance among the resin components listed as the base material layer of the gas barrier film. Examples of such resin components include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, and aromatic resin. Examples thereof include polymers and polyurethane-based polymers.
In addition, these resins can be used individually by 1 type or in combination of 2 or more types. Moreover, you may also use the film which colored these. By coloring, the presence or absence of the protective film can be easily determined, and the interface between the gas barrier film and the protective film can be easily recognized, which is convenient when peeling off the protective film.

The thickness of the protective layer of the protective film may be sufficient to protect the gas barrier film, and is preferably 1 to 500 μm, more preferably 5 to 200 μm, and further preferably 10 to 100 μm.

The ratio of the thickness of the protective layer of the protect film to the thickness of the base material layer of the gas barrier film (thickness of the protect layer / thickness of the base material layer) is that of the gas barrier laminate while thinning the base material layer. From the viewpoint of improving handleability, it is preferably 1 to 5, more preferably 1.2 to 4.5, and even more preferably 1.5 to 4.

<Adhesive layer>
The adhesive layer of the protective film is a layer that is laminated on one surface of the protective layer and is used for bonding the protective layer and the gas barrier film.
Here, in the gas barrier laminate of the present invention, the adhesive force b between the gas barrier film and the protective film is preferably adjusted to be low from the viewpoint of satisfying the relationship of the above formula (1).
The adhesive strength b between the gas barrier film and the protective film can be adjusted to be low by lowering the adhesiveness of the adhesive layer of the protective film.
Examples of the method of lowering the adhesiveness of the pressure-sensitive adhesive layer of the protective film include reducing the thickness of the pressure-sensitive adhesive layer and changing the type of the pressure-sensitive adhesive layer. The adhesive layer of the gas barrier laminate of the present invention must be provided with the properties necessary for sealing the object to be sealed. Therefore, rather than changing the adhesive force a by adjusting the type of raw material and the amount of the raw material blended in the adhesive composition for forming the adhesive layer, it is only necessary to control the adhesion property to the gas barrier film. It is easier to change the adhesive force b by adjusting the adhesiveness of.

The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 40 μm, and further preferably 1 μm to 25 μm from the viewpoint of reducing the stickiness of the pressure-sensitive adhesive layer.

The type of the pressure-sensitive adhesive layer can be changed by selecting a resin which is a polymer contained in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. Hereinafter, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer will be described with reference to the selection of the resin as the polymer.

<Adhesive composition>
The pressure-sensitive adhesive composition, which is a material for forming the pressure-sensitive adhesive layer, contains a resin (X) which is a polymer.
The resin (X) may or may not have adhesiveness by itself. When the resin (X) does not have adhesiveness, a tackifier described later is added to the adhesive composition so that the adhesive layer formed from the adhesive composition exhibits adhesiveness. May be good.
In one aspect of the present invention, the components other than the resin (X) contained in the pressure-sensitive adhesive composition can be appropriately adjusted as needed.
For example, in one aspect of the present invention, from the viewpoint of adjusting the adhesive strength to a desired range, the pressure-sensitive adhesive composition may further contain one or more selected from the group consisting of a pressure-sensitive adhesive and a cross-linking agent. In addition to these, one or more selected from the group consisting of a diluting solvent and an additive for a pressure-sensitive adhesive used for a general pressure-sensitive adhesive may be contained.

(Resin (X))
The weight average molecular weight (Mw) of the resin (X) is preferably 10,000 or more, more preferably 10,000 to 2 million, and even more preferably 20,000 to 1.5 million.
Examples of the resin (X) contained in the pressure-sensitive adhesive composition include acrylic resin, urethane resin, olefin resin, acrylic urethane resin, polyester resin and the like.
These resins (X) can be used alone or in combination of two or more.
When these resins (X) are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and block copolymers, random copolymers, and grafts are used. It may be any of the copolymers.
Here, the resin (X) is made of acrylic from the viewpoint of appropriately adjusting the adhesiveness of the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition and adjusting the adhesive strength b between the gas barrier film and the protective film to be low. Based resins and olefin resins are preferable, and acrylic resins are more preferable.

The content of the resin (X) in the pressure-sensitive adhesive composition is preferably 30 to 99.99% by mass, more preferably 40 to 99.95% by mass, based on the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition. %, More preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, still more preferably 60 to 99.50% by mass.
Hereinafter, in one aspect of the present invention, a preferable acrylic resin and olefin resin as the resin (X) will be described.

(Acrylic resin)
In one aspect of the present invention, from the viewpoint of appropriately adjusting the adhesiveness of the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition to lower the adhesive force b between the gas barrier film and the protective film, the pressure-sensitive adhesive composition It is preferable that the resin (X) contained in the product contains an acrylic resin.
The content ratio of the acrylic resin in the resin (X) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total amount (100% by mass) of the resin (X) contained in the pressure-sensitive adhesive composition. %, More preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass.

Examples of the acrylic resin that can be used as the resin (X) include a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a (meth) acrylate having a cyclic structure. Examples thereof include a polymer containing a derived structural unit.

The weight average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 130,000 to 1,300,000.

As the acrylic resin, an acrylic polymer (A0) having a structural unit (a1) derived from an alkyl (meth) acrylate (a1') (hereinafter, also referred to as "monomer (a1')") is preferable. A polypolypolymer (A1) having a structural unit (a2) derived from a functional group-containing monomer (a2') (hereinafter, also referred to as "monomer (a2')") together with the unit (a1) is more preferable.

The number of carbon atoms of the alkyl group contained in the monomer (a1') is preferably 1 to 24, more preferably 1 to 12, from the viewpoint of making it easier to adjust the adhesive strength to be low as the pressure-sensitive adhesive layer is thinned. ..
The alkyl group contained in the monomer (a1') may be a straight chain alkyl group or a branched chain alkyl group.

Examples of the monomer (a1') include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (). Examples thereof include meta) acrylate and stearyl (meth) acrylate.
As the monomer (a1'), methyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable.
These monomers (a1') can be used alone or in combination of two or more.
Among these, the monomer (a1') is preferably used in combination with butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
Further, these mass ratios [butyl (meth) acrylate / 2-ethylhexyl (meth) acrylate] are preferably from 1/9 from the viewpoint of making it easy to adjust the adhesive force b between the gas barrier film and the protective film to be low. It is 5/5, more preferably 1/9 to 4/6, and even more preferably 1/9 to 3/7.

The content of the structural unit (a1) is preferably 50 to 100% by mass, more preferably 60 to 60 to 100% by mass, based on all the structural units (100% by mass) of the acrylic polymer (A0) or the acrylic copolymer (A1). It is 99.9% by mass, more preferably 70 to 99.5% by mass, and even more preferably 80 to 99.0% by mass.

The functional group contained in the monomer (a2') refers to a functional group capable of reacting with a cross-linking agent which may be contained in the pressure-sensitive adhesive composition described later and serving as a cross-linking starting point or a functional group having a cross-linking promoting effect, for example, a hydroxyl group. Examples thereof include a carboxy group, an amino group and an epoxy group.
That is, examples of the monomer (a2') include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
These monomers (a2') can be used alone or in combination of two or more.
As the monomer (a2'), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate. ) Hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid and their anhydrides. 2- (Acryloyloxy) ethyl succinate, 2-carboxyethyl (meth) acrylate and the like can be mentioned.
As the monomer (a2'), 2-hydroxyethyl (meth) acrylate is preferable.
These monomers (a2') can be used alone or in combination of two or more.

The content of the structural unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.3 to 30% by mass, based on the total structural units (100% by mass) of the acrylic copolymer (A1). It is more preferably 0.5 to 20% by mass, and even more preferably 0.7 to 10% by mass. As the content of the structural unit (a2) serving as the starting point of crosslinking increases, the adhesive force b between the gas barrier film and the protective film tends to decrease.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').
In the acrylic copolymer (A1), the contents of the structural units (a1) and (a2) are preferably 70 to 100 in the total structural units (100% by mass) of the acrylic copolymer (A1). It is by mass, more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, and even more preferably 90 to 100% by mass.

Examples of the monomer (a3') include olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate. (Meta) Acrylate; Examples thereof include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholine, and N-vinylpyrrolidone.
These monomers (a3') can be used alone or in combination of two or more.
As the monomer (a3'), vinyl acetate is preferable.

(Olefin resin)
The olefin-based resin that can be used as the resin (X) is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
The olefin-based resin may be used alone or in combination of two or more.
Specific examples of the olefin-based resin include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, a copolymer of ethylene and propylene, and ethylene and other α-. Copolymer with olefin, copolymer of propylene and other α-olefin, copolymer of ethylene and propylene and other α-olefin, common weight of ethylene and other ethylenically unsaturated monomer Examples thereof include a coalescence (ethylene-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, ethylene-vinyl alcohol copolymer, etc.). Among these, an ethylene-vinyl acetate copolymer, which is a copolymer of ethylene and another ethylenically unsaturated monomer, is preferable.
Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like. Be done.
Examples of the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth) acrylate, vinyl alcohol and the like.

The olefin resin may be a rubber resin. Examples of the rubber-based resin that can be used as the resin (X) include polyisobutylene-based resins. The polyisobutylene resin (hereinafter, also referred to as “PIB resin”) is not particularly limited as long as it is a resin having a polyisobutylene skeleton in at least one of the main chain and the side chain.
The number average molecular weight (Mn) of the PIB-based resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, still more preferably 50,000 to 800,000, and even more preferably 70,000 to 600,000.

Examples of the PIB-based resin include polyisobutylene, which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers. Examples thereof include butyl gum halide that has been brominated or chlorinated. Among these, a copolymer of isobutylene and isoprene is preferable.

When the PIB-based resin is a copolymer, it is assumed that the structural unit composed of isobutylene is contained in the largest amount among all the structural units.
The content of the structural unit composed of isobutylene is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, based on all the structural units (100 mol%) of the PIB-based resin. be.
These PIB-based resins can be used alone or in combination of two or more.

When a PIB-based resin is used, it is preferable to use a rubber-based resin capable of cross-linking reaction, such as polyisoprene rubber having a carboxylic acid-based functional group.

(Crosslinking agent)
In one aspect of the present invention, the pressure-sensitive adhesive composition is a resin (X) having the above-mentioned functional groups such as an acrylic copolymer having the above-mentioned structural units (a1) and (a2) and a rubber-based resin capable of cross-linking. ), It is preferable to further contain a cross-linking agent.
The cross-linking agent reacts with the functional group of the resin (X) to cross-link the resins. The adhesive strength b between the gas barrier film and the protective film can be adjusted by the degree of cross-linking between the resins.

Examples of the cross-linking agent include isocyanate-based cross-linking agents such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and their adducts; ethylene glycol glycidyl ether, 1,3-bis (N, N-diglycidyl-amino). Epoxy-based cross-linking agents such as methyl) cyclohexane; isocyanate-based cross-linking agents such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; chelate-based cross-linking agents such as aluminum chelate; and the like.
These cross-linking agents may be used alone or in combination of two or more.
Among these cross-linking agents, isocyanate-based cross-linking agents are preferable from the viewpoint of making it easy to adjust the adhesive strength to be low as the pressure-sensitive adhesive layer is thinned and the availability.

The content of the cross-linking agent is appropriately adjusted according to the number of functional groups of the resin (X). For example, 100 parts by mass of the resin (X) having the above-mentioned functional groups such as the acrylic copolymer. On the other hand, it is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and further preferably 0.05 to 4 parts by mass. Since the content of the cross-linking agent is high and the cross-linking density in the pressure-sensitive adhesive layer is high, the adhesive strength b between the gas barrier film and the protective film tends to be low.

(Adhesive)
In one aspect of the present invention, the pressure-sensitive adhesive composition may further contain a pressure-sensitive adhesive together with the resin (X).
As the tackifier, the same tackifier as the tackifier (E) described above can be used.
The content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, still more preferably 0.1 to 50% by mass, based on the total amount of the pressure-sensitive adhesive composition. It is more preferably 0.5 to 45% by mass, and even more preferably 1.0 to 40% by mass.

(Additives for adhesives)
In one aspect of the present invention, the pressure-sensitive adhesive composition contains a pressure-sensitive adhesive additive used in general pressure-sensitive adhesives other than the above-mentioned pressure-sensitive adhesive and cross-linking agent, as long as the effects of the present invention are not impaired. May be.
Examples of the adhesive additive include antioxidants, softeners (plasticizers), rust inhibitors, retarders, catalysts, ultraviolet absorbers, reaction accelerators, reaction inhibitors and the like.
It should be noted that these adhesive additives may be used alone or in combination of two or more.
When these additives for adhesives are contained, the content of each additive for adhesives is independently, preferably 0.0001 to 20 parts by mass, more preferably 0.0001 to 20 parts by mass with respect to 100 parts by mass of the resin (X). Is 0.001 to 10 parts by mass.

(Diluting solvent)
In one aspect of the present invention, the pressure-sensitive adhesive composition may contain water or an organic solvent as a diluting solvent together with the above-mentioned various active ingredients, and may be in the form of a solution.
Examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, tert-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane. And so on.
As these diluting solvents, one type can be used alone, or two or more types can be used in combination.

When the pressure-sensitive adhesive composition contains a diluting solvent and is in the form of a solution, the concentration of the active ingredient of the pressure-sensitive adhesive composition is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and further preferably 10. It is ~ 50% by mass, more preferably 25 to 45% by mass, and even more preferably 30 to 45% by mass.

[Peeling sheet]
As the release sheet, a conventionally known one can be used. For example, a material having a release layer that has been peeled with a release agent on a base material for a release sheet can be mentioned.
Examples of the base material for the release sheet include paper base materials such as glassin paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; polyethylene terephthalate resin and polybutylene terephthalate resin. , Polyethylene naphthalate resin, polypropylene resin, plastic film formed from polyethylene resin, etc .; and the like.
These can be used alone or in combination of two or more. Further, the base material for the release sheet may be a laminated body in which two or more of these are laminated.
Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
These can be used alone or in combination of two or more.

[Manufacturing method of gas barrier laminate]
The method for producing the gas barrier laminate is not particularly limited.
For example, in the method for producing an adhesive layer described above, a gas barrier film is attached to the surface of the adhesive layer on which a release sheet is not provided, and the adhesive layer of the protective film and the gas barrier film are attached to each other to form a gas barrier. A sex laminate can be produced.
When the protect film is a single layer of the protect layer, the gas barrier laminate can be manufactured by laminating the protect layer and the gas barrier film. For example, the self-adhesiveness of the protective film allows the protective layer to be laminated on the gas barrier film.

[Encapsulant]
The sealed body is formed by sealing the material to be sealed by laminating the surface of the exposed adhesive layer and the material to be sealed to cover the material to be sealed.
Examples of the object to be sealed include electronic devices such as an organic EL element, an organic EL display element, a liquid crystal display element, and a solar cell element.

Here, the object to be sealed may be mounted on a substrate such as a transparent substrate.
When the material to be sealed is mounted on a substrate such as a transparent substrate, the curable adhesive layer of the gas barrier laminate covers the surface of the material to be sealed and the surface of the substrate around the material to be sealed. It is attached so as to cover it.
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. Further, a material having high blocking performance to block water vapor and gas that try to enter 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, acetylcellulose, brominated phenoxy, aramids, polyimides, etc. Transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins; and the like.
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 element.

[Manufacturing method of sealed body]
The method for producing the sealed body is not particularly limited. For example, a sealed body can be obtained by at least covering the surface of the object to be sealed with an adhesive layer of a gas barrier laminated body. When the adhesive layer of the gas barrier laminate is a curable adhesive layer, the adhesive layer of the gas barrier laminate is cured by performing a curing treatment such as heating or energy ray irradiation. The adhesiveness to the surface of the sealed material can be improved. The step of peeling the protective film from the gas barrier laminate and removing it is a process of sealing the object to be sealed with the gas barrier laminate to prepare a sealed body, and a process of processing and transporting the sealed body. It may be either. According to the gas barrier laminate of the present invention, no gap is formed between the object to be sealed and the adhesive layer even if the protective film is peeled from the gas barrier laminate at any timing. Therefore, deterioration of the object to be sealed due to the infiltration of moisture, oxygen, etc. is prevented.
That is, in one aspect of the present invention, it is preferable that the method for producing the sealed body includes the following steps (1) and (2) in this order.
-Step (1): A step of attaching the gas-barrier laminate of the present invention to an object to be sealed with an adhesive layer as a bonding surface-Step (2): A step of peeling a protective film from the gas-barrier laminate. When the adhesive layer of the gas barrier laminate is a curable adhesive layer, the step of peeling and removing the protective film from the gas barrier laminate is performed after the adhesive layer is cured, even before the adhesive layer is cured. There may be.
When the adhesive layer is cured by heating, the protective film has a gas barrier property from the viewpoint of preventing defects due to changes in the characteristics and shape of the protective layer and the adhesive layer of the protective film due to the heat generated when the adhesive layer is cured. The step of peeling and removing from the laminate is preferably before curing the adhesive layer.
Further, even when the adhesive layer is cured by irradiation with energy rays, the protective film has a gas barrier property from the viewpoint of suppressing a decrease in the energy dose irradiated to the adhesive layer by the protective layer or the adhesive layer of the protective film. The step of peeling and removing from the laminate is preferably before curing the adhesive layer.
That is, in one aspect of the present invention, it is preferable that the method for producing the sealed body includes the following steps (1) to (3) in this order.
-Step (1): A step of attaching the gas barrier laminate of the present invention to an object to be sealed with a curable adhesive layer as a bonding surface.-Step (2): Peeling the protective film from the gas barrier laminate. Step / Step (3): Step of curing the curable adhesive layer The curing treatment in the step (3) may be heating or energy ray irradiation.
In the gas barrier laminate of the present invention, the adhesive force a between the glass plate and the curable adhesive layer and the adhesive force b between the gas barrier film and the protective film satisfy the above formula (1). Therefore, even before the adhesive layer is cured, the protective film can be peeled off without creating a gap between the object to be sealed and the adhesive layer.

The bonding conditions for bonding the adhesive layer of the gas barrier laminate and the object to be sealed are not particularly limited. The temperature at the time of sticking is, for example, 10 to 60 ° C, preferably 20 to 45 ° C. This bonding process may be performed while pressurizing. When the adhesive layer of the gas barrier laminate is a thermosetting adhesive layer, the curing conditions for curing the thermosetting adhesive layer are not particularly limited. For example, when the polyolefin resin (A) is an acid-modified polyolefin resin, 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). Is 1 to 6 hours).
When the adhesive layer of the gas barrier laminate is an energy ray-curable adhesive layer, the curing conditions for curing the energy ray-curable adhesive layer are not particularly limited. For example, using ultraviolet rays as energy rays, the adhesive layer can be irradiated with ultraviolet rays at an ^{irradiance of 20 to 1000 mW / cm 2} and a light intensity of about 50 to 1000 mJ / cm ^{2, and the irradiation time is usually 0.1.} ~ 1000 seconds, preferably 1 to 500 seconds.

The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.

[Film thickness]
(1) Thickness of Anchor Coat Layer The film thickness was measured using a film thickness measuring device (manufactured by Filmometrics Co., Ltd., product name "F20").
(2) Thickness of gas barrier layer Measured using a spectroscopic ellipsometer (manufactured by JA Woolam Japan Co., Ltd., product name "M-2000").
(3) Measurement of the thickness of each layer other than the anchor coat layer and the gas barrier layer Using a constant pressure thickness measuring instrument (model number: "PG-02J", standard: JIS K6783, Z1702, Z1709) manufactured by Teclock Co., Ltd. Was measured.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) of the modified polyolefin resin (A1) used as the raw material of the curable adhesive layer and the polyfunctional epoxy compound (B2) used as the curable component (B). The weight average molecular weight (Mw) of the above, the weight average molecular weight (Mw) of the acrylic resin which is the raw material of the pressure-sensitive adhesive layer of the protective film, and the number average molecular weight (Mn) of the PIB resin are values measured by the following methods. Is.

(1) Weight average molecular weight (Mw) of modified polyolefin resin (A1), weight average molecular weight (Mw) of acrylic resin, number average molecular weight (Mn) of PIB resin.
Measured under the following conditions using a gel permeation chromatograph (GPC) device (manufactured by Tosoh Corporation, product name "HLC-8320"), and converted to the weight average molecular weight and number average molecular weight of standard polystyrene. board.
(Measurement condition)
-Measurement sample: Tetrahydrofuran solution with a sample concentration of 1% by mass-Column: Two "TSK gel Super HM-H" and one "TSK gel Super H2000" (both manufactured by Tosoh Corporation) are connected in sequence. Column temperature: 40 ° C
・ Developing solvent: tetrahydrofuran ・ Flow rate: 0.60 mL / min

(2) Weight average molecular weight (Mw) of the polyfunctional epoxy compound (B2)
Measured under the above conditions using the above gel permeation chromatograph (GPC) apparatus, the weight average of standard polystyrene corresponding to the retention time of the peak top of the peak having the largest area among the plurality of observed peaks. The value was converted to the molecular weight.

[Preparation of gas barrier laminate]
The gas barrier film, the curable adhesive layer, and the protective film described below were prepared, and these were laminated to prepare 18 kinds of gas barrier laminates 1 to 18.

(1) Preparation of gas barrier film Polyethylene terephthalate (manufactured by Toray Industries, Inc., PET50A4100, thickness: 50 μm) is used as a base material layer, and one side (smooth surface not easily adhered) of the base material layer is exposed to ultraviolet rays (UV). A composition containing a curable resin and reactive silica (manufactured by JSR Corporation, product name "Opstar Z7530") was applied with a Meyer bar to form a coating film, and the coating film was dried at 70 ° C. for 1 minute. Then, using a conveyor type UV light irradiation device (manufactured by Fusion Co., Ltd., product name "F600V"), the coating film is irradiated with UV under the following conditions to cure the coating film, and an anchor having a thickness of 1 μm. A coat layer was formed.
(UV irradiation conditions)
・ UV lamp: High-pressure mercury lamp ・ Line speed: 20 m / min ・ Integrated light intensity: 120 mJ / cm ²
・ Illuminance: 200mW / cm ²
・ Lamp height: 104 mm

Next, a coating material containing perhydropolysilazane as a main component (manufactured by Clariant Japan Co., Ltd., trade name "Aquamica NL110-20") was applied to the surface of the anchor coat layer by a spin coating method, and heated at 120 ° C. for 1 minute. A polysilazane layer containing perhydropolysilazane was formed. The thickness of the polysilazane layer was 200 nm.
Next, argon (Ar) was implanted into the surface of the polysilazane layer by plasma ions using a plasma ion implantation device to form a gas barrier layer, thereby producing a gas barrier film 1 having the following laminated structure.
(Laminated structure of gas barrier film 1)
・ Base material layer / anchor coat layer / gas barrier layer

(2) Formation of Adhesive Layer As the adhesive layer, three types of thermosetting adhesive layers 1 to 3 described below were formed.

(2-1) Formation of Thermosetting Adhesive Layer 1 100 parts by mass of polyolefin resin (A), 27 parts by mass of curable component (B), 0.1 parts by mass of silane coupling agent (C), curing catalyst (D) 0.6 parts by mass was dissolved in methyl ethyl ketone to prepare an adhesive composition 1 having a solid content concentration of 20% by mass.
The polyolefin resin (A) used in the preparation of the adhesive composition 1, the thermosetting component (B-1) used as the curable component (B), the silane coupling agent (C), and the curing catalyst (D). ) Is shown below.
-Polyolefin-based resin (A): manufactured by Mitsui Chemicals, Inc., product name "Unistor H-200", acid-modified α-olefin polymer, solid at 25 ° C., weight average molecular weight (Mw) = 52,000, modified polyolefin It is a resin corresponding to the system resin (A1).
Thermosetting component (B-1): manufactured by Mitsubishi Chemical Corporation, product name "YX8034", hydrogenated bisphenol A diglycidyl ether, liquid at 25 ° C., epoxy equivalent = 270 g / eq, weight average molecular weight (Mw) = It is a compound corresponding to a polyfunctional epoxy compound (BL) that is liquid at 3,200 and 25 ° C.
-Silane coupling agent (C): glycidoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-4803"
-Curing catalyst (D): 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Corporation, product name "Curesol 2E4MZ"

The prepared adhesive composition 1 is applied onto the peeling-treated surface of a peeling sheet (manufactured by Lintec Corporation, trade name "SP-PET38131"), and the obtained coating film is heated at 100 ° C. for 2 minutes to obtain a thickness. Formed a thermosetting adhesive layer 1 of 10 μm.

(2-2) Formation of Thermosetting Adhesive Layer 2 In the above "(2-1) Formation of Thermosetting Adhesive Layer 1", the thermosetting component (B-1) is shown below. The adhesive composition 2 was prepared by changing to the thermosetting component (B-2), and the thermosetting adhesive layer 2 was formed.
Thermosetting component (B-2): manufactured by Mitsubishi Chemical Corporation, product name "YX8000", hydrogenated bisphenol A diglycidyl ether, liquid at 25 ° C, epoxy equivalent = 205 g / eq, weight average molecular weight (Mw) = It is a compound corresponding to a polyfunctional epoxy compound (BL) that is liquid at 1,400 and 25 ° C.

(2-3) Formation of Thermosetting Adhesive Layer 3 100 parts by mass of polyolefin resin (A), 90 parts by mass of curable component (B), 0.1 parts by mass of silane coupling agent (C), curing catalyst 1.2 parts by mass of (D) and 50 parts by mass of the tackifier (E) were dissolved in methyl ethyl ketone to prepare an adhesive composition 3 having a solid content concentration of 28% by mass.
The polyolefin resin (A), the silane coupling agent (C), and the curing catalyst (D) were the same as those used in "(2-1) Formation of thermosetting adhesive layer 1" above.
The curable component (B) was the thermosetting component (B-2) used in the above-mentioned "(2-2) Formation of the thermosetting adhesive layer 2".
The tackifier (E) was a copolymer of a styrene-based monomer and an aliphatic monomer (manufactured by Mitsui Chemicals, Inc., product name "FTR6100", softening point = 95 ° C.).
Other than that, the thermosetting adhesive layer 3 was formed by the same method as the above-mentioned "(2-1) Formation of the thermosetting adhesive layer 1".

(3) Preparation of Protective Films Six types of protective films 1 to 6 described below were prepared.

(3-1) Preparation of Protect Film 1 A polyethylene-based film (manufactured by Sun A. Kaken Co., Ltd., product name "PAC-3-70") was designated as Protect Film 1.
(Structure of Protect Film 1)
-Adhesive layer (ethylene-vinyl alcohol copolymer) / protect layer (low density polyethylene film)

(3-2) Preparation of Protect Film 2 (meth) acrylic by copolymerizing 20 parts by mass of n-butyl acrylate, 80 parts by mass of 2-ethylhexyl acrylate, and 2.5 parts by mass of 2-hydroxyethyl acrylate. An acid ester copolymer (weight average molecular weight Mw = 160,000) was prepared.
Next, 100 parts by mass of the (meth) acrylic acid ester copolymer, 3.4 parts by mass of an isocyanate-based cross-linking agent (hexamethylene diisocyanate), and 0.010 parts by mass of a reaction accelerator (dioctyltin dilaurate) were reacted. 1.0 part by mass of an inhibitor (acetylacetone) was mixed, and the mixture was sufficiently stirred and diluted with methyl ethyl ketone to obtain a pressure-sensitive adhesive composition having a solid content concentration of 37% by mass.
The pressure-sensitive adhesive composition was applied to a peeling sheet (manufactured by Lintec Corporation, product name "SP-PET38131", thickness: 38 μm) in which one side of a polyethylene terephthalate film was peeled off with a silicone-based release agent. It was applied with a coater to form a coating film. The coating film was heat-treated at 90 ° C. for 1 minute to form an adhesive layer having a thickness of 20 μm. As a result, a laminated body composed of an adhesive layer and a release sheet was obtained.
Next, the pressure-sensitive adhesive layer of the laminate and one side of a polyethylene terephthalate film (manufactured by Toray Advanced Materials Korea, product name "XD571S", tensile modulus at 23 ° C.: 3.9 GPa, thickness: 38 μm) are bonded together. By doing so, a protective film 2 having the following laminated structure was produced.
(Structure of Protect Film 2)
-Release sheet / adhesive layer (thickness: 20 μm, acrylic resin) / protect layer (thickness: 38 μm, polyethylene terephthalate film)

(3-3) Preparation of Protect Film 3 The thickness of the adhesive layer of the Protect Film 2 was changed to 10 μm to prepare the Protect Film 3.
(Structure of Protect Film 3)
-Release sheet / adhesive layer (thickness: 10 μm, acrylic resin) / protect layer (thickness: 38 μm, polyethylene terephthalate film)

(3-4) Preparation of Protect Film 4 Copolymer of isoprene and isoprene (manufactured by Nippon Butyl Co., Ltd., product name "Exxon Butyl 268", number average molecular weight 260,000, isoprene content: 1.7 mol%) 100 parts by mass, 5 parts by mass of polyisoprene rubber having a carboxylic acid-based functional group (manufactured by Kuraray Co., Ltd., product name "LIR410", number average molecular weight 30,000, average number of carboxyl groups per molecule: 10), and fat 20 parts by mass of group petroleum resin (manufactured by Nippon Zeon Co., Ltd., product name "Quinton A100", softening point 100 ° C.) and 1 mass of cross-linking agent (manufactured by Mitsubishi Chemical Co., Ltd., product name "TC-5", epoxy compound) The parts were dissolved in toluene to obtain a pressure-sensitive adhesive composition having a solid content concentration of 25% by mass.
Using the pressure-sensitive adhesive composition, the protect film 4 was produced in the same manner as in the above-mentioned "(2) Protect film 2" except that the thickness of the pressure-sensitive adhesive layer was adjusted to 2 μm.
(Structure of Protect Film 4)
-Release sheet / adhesive layer (thickness: 2 μm, PIB resin) / protect layer (thickness: 38 μm, polyethylene terephthalate film)

(3-5) Preparation of Protect Film 5 The thickness of the adhesive layer of the Protect Film 4 was changed to 10 μm to prepare the Protect Film 5.
(Structure of Protect Film 5)
-Release sheet / adhesive layer (thickness: 10 μm, PIB resin) / protect layer (thickness: 38 μm, polyethylene terephthalate film)

(3-6) Preparation of Protect Film 6 A weakly adhesive adhesive sheet (manufactured by Lintec Corporation, product name "PF-PET38C") was used as the protective film 6.
(Structure of Protect Film 6)
-Adhesive layer (acrylic resin) / protect layer (polyethylene terephthalate film)

(4) Preparation of Gas Barrier Laminated Body The gas barrier layer of the gas barrier film 1 produced in the above "(1) Preparation of the gas barrier film" and the thermosetting adhesion formed in the above "(2) Formation of the adhesive layer" The agent layers 1 to 3 were bonded together. Then, on the barrier film side (base material layer surface), the protective films 1 to 3 prepared in the above "(3) Preparation of protective film" under the conditions of a temperature of 23 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. 6 is laminated with the pressure-sensitive adhesive layer as the bonding surface, and the gas barrier film 1, the thermosetting adhesive layers 1 to 3 and the protect films 1 to 6 are laminated in the combination shown in Table 1. Body 1-18 was made.

[Examples 1 to 15, Comparative Examples 1 to 3]
The following measurements and evaluations were carried out for the gas barrier laminates 1 to 15 of Examples 1 to 15 and the gas barrier laminates 16 to 18 of Comparative Examples 1 to 3 shown in Table 1.

(1) Measurement of Adhesive Strength b of Protect Film to Gas Barrier Film The release sheet of the gas barrier laminate cut to a width of 50 mm and a length of 20 mm is peeled off, and a thermosetting adhesive layer is used as a bonding surface to form a soda lime glass plate. A gas barrier laminate was laminated on the surface. A laminating device equipped with a roller (a roll-type multi-laminator manufactured by Japan Office Laminator Co., Ltd.) was used for laminating, and the laminating conditions were a temperature of 23 ° C., a pressure of 0.2 MPa, and a speed of 2.0 m / min.
After laminating, 50% R. at 23 ° C. H. The film was allowed to stand in a (relative humidity) environment for 24 hours, and in the same environment, the protective film was peeled off from the gas barrier film at a peeling angle of 180 °, and the 180 ° peeling adhesive strength measurement test (N / 50 mm, Peeling speed: 300 mm / min) was carried out, and the adhesive force b between the gas barrier film and the protective film was measured. In the appearance evaluation described later, for those in which floating occurred, a thermosetting adhesive layer of the gas barrier laminate was attached to a soda lime glass plate via double-sided tape and measured again to determine the adhesive strength b. It was measured.

(2) Appearance evaluation When measuring the adhesive strength b between the gas barrier film and the protective film, is there any floating between the soda lime glass plate, which is the adherend, and the thermosetting adhesive layer? It was confirmed visually. The case where no float was observed was designated as "A", and the case where float occurred was designated as "F".

(3) Measurement of adhesive force a between the glass plate and the thermosetting adhesive layer Peel off the release sheet of the gas barrier laminate cut to a width of 50 mm and a length of 20 mm, and attach the thermosetting adhesive layer. As a mating surface, a gas barrier laminate was laminated on a soda lime glass plate. A laminating device equipped with a roller (a roll-type multi-laminator manufactured by Japan Office Laminator Co., Ltd.) was used for laminating, and the laminating conditions were a temperature of 23 ° C., a pressure of 0.2 MPa, and a speed of 2.0 m / min.
After laminating, 50% R. at 23 ° C. H. It was allowed to stand in an environment of (relative humidity) for 24 hours, and in the same environment, the gas barrier laminate was peeled off from the soda lime glass plate at a peeling angle of 180 °, and 180 ° peeling adhesive strength measurement test ( N / 50 mm, peeling speed: 300 mm / min) was carried out, and the adhesive force a between the glass plate and the thermosetting adhesive layer was measured.

The results are shown in Table 1.

From Table 1, the following can be seen.
As in Examples 1 to 15, it can be seen that the gas barrier laminates in which a> b are not floated and have a good appearance.
On the other hand, as in Comparative Examples 1 to 3, it can be seen that the gas barrier laminate in which a <b is floating is observed and the appearance is poor.

Claims (14)

An adhesive layer, a gas barrier film, and a protective film are gas barrier laminated bodies having a laminated structure arranged in this order.
The gas barrier laminate is pressed against a glass plate by a roller under the following condition (α) with the adhesive layer as a bonding surface, and after the gas barrier laminate and the glass plate are bonded, the following conditions (α) Peeling with β), the other conditions are measured in accordance with JIS Z0237: 2000, between the adhesive force a between the glass plate and the adhesive layer and between the gas barrier film and the protective film. A gas barrier laminate whose adhesive strength b satisfies the following formula (1).
a> b ... (1)
Condition (α): temperature 23 ° C., pressure 0.2 MPa, and speed 0.2 m / min
Condition (β): After application, leave for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then peel off at a peeling speed of 300 mm / min. The gas barrier laminate according to claim 1, wherein the adhesive layer is a curable adhesive layer. The gas barrier laminate according to claim 2, wherein the adhesive layer is a layer formed from an adhesive composition containing a polyolefin resin (A). The gas barrier laminate according to claim 3, wherein the polyolefin-based resin (A) contains a modified polyolefin-based resin (A1). Any of claims 2 to 4, wherein the curable adhesive layer contains a curable component (B), and the curable component (B) contains a polyfunctional epoxy compound (BL) that is liquid at 25 ° C. The gas barrier laminate according to item 1. The gas barrier laminate according to claim 5, wherein the polyfunctional epoxy compound (BL) has a weight average molecular weight (Mw) of 1,500 or more and 5,000 or less. The gas barrier laminate according to claim 5 or 6, wherein the content of the polyfunctional epoxy compound (BL) is 10 to 34% by mass based on the total amount of the adhesive composition. The gas-barrier laminate according to any one of claims 1 to 7, wherein the gas barrier film has a base material layer and a gas barrier layer. The gas barrier laminate according to claim 8, wherein the base material layer has a resin film containing at least one selected from polycarbonate, a cycloolefin polymer, and a cycloolefin copolymer as a resin component. The gas barrier laminate according to claim 8 or 9, wherein the base material layer has a thickness of 30 μm or less. The gas barrier laminate according to any one of claims 8 to 10, wherein the gas barrier layer is a polymer layer containing a polymer compound and subjected to a modification treatment. The gas-barrier laminate according to any one of claims 8 to 11, wherein the gas barrier layer and the adhesive layer are directly laminated. The gas barrier laminate according to any one of claims 1 to 12, wherein the protect film has a protect layer and an adhesive layer, and the adhesive layer is attached to the gas barrier film. A method for producing a sealed body, which comprises the following steps (1) and (2) in this order.
-Step (1): Step of attaching the gas barrier laminate according to any one of claims 1 to 13 to an object to be sealed with an adhesive layer as a bonding surface-Step (2): Protecting film Step of peeling from the gas barrier laminate