JP7356442B2 - Gas barrier laminate - Google Patents

Description

The present invention relates to a gas barrier laminate.

In recent years, organic EL elements have attracted attention as light emitting elements capable of emitting high-intensity light by low-voltage DC drive.
However, organic EL devices have a problem in that their light emitting characteristics tend to deteriorate over time. This problem is thought to be caused by oxygen, moisture, and the like entering the organic EL element and deteriorating the electrodes and organic layers. Therefore, as a countermeasure to this problem, organic EL elements are sealed with a sealing material to prevent the infiltration of oxygen, moisture, and the like.
Specifically, a method has been proposed in which an object to be sealed, such as an organic EL element, is sealed with a gas barrier sealing material having a layered structure. Patent Document 1 describes a technique for sealing an organic EL element using a sealing film in which a gas barrier film is laminated on an adhesive film.

Japanese Patent Application Publication No. 2007-197517

Objects to be sealed, such as electronic devices such as organic EL elements, that need to be prevented from deteriorating due to oxygen, moisture, etc., have an adhesive layer and a sealing film having the layer structure described in Patent Document 1. It may be sealed with a gas barrier laminate having a laminate structure in which a gas barrier film is laminated.

By the way, the process of storing and transporting the gas barrier laminate until it is used, the process of manufacturing a sealed body by sealing an object with the gas barrier laminate, and the processing and transportation of the sealed body, etc. In the process, the gas barrier film is placed on the outermost surface. Therefore, scratches and cracks may occur in the gas barrier film, and the gas barrier properties of the gas barrier film may deteriorate. In addition, when the object to be sealed is a light emitting element such as an organic EL element and used for a display or other purpose, if the gas barrier film is scratched or cracked, the scratch or crack becomes a defect and causes bright spots to occur. Sometimes it becomes.

Therefore, the present inventors investigated the process of storing and transporting the gas barrier laminate until it is used, the process of sealing the object to be sealed with the gas barrier laminate to produce a sealed body, and the process of manufacturing the sealed body. In order to prevent the gas barrier film from being scratched or cracked during the process of processing and transporting the body, we considered protecting the entire surface of the gas barrier film with a protective film and peeling off the protective film at the desired timing. . The desired timing means, for example, the timing when the gas barrier film no longer needs to be protected or the timing when it becomes necessary to expose the gas barrier film.
However, it has become clear that when the protect film is peeled off after the object to be sealed is sealed with the gas barrier laminate, a gap may occur between the object to be sealed and the adhesive layer. If a gap occurs between the object to be sealed and the adhesive layer, oxygen, moisture, etc. may enter through the gap, causing deterioration of the object to be sealed. Moreover, the appearance is also poor. On the other hand, in a sealed body sealed with a gas barrier laminate, even if there is no gap between the sealed object and the adhesive layer, the sealed object may be damaged due to various factors. There is also a possibility that oxygen, moisture, etc. may enter and cause deterioration of the object to be sealed.

The present invention has been made in view of such problems, and includes steps such as storage and transportation of the gas barrier laminate before use, and sealing of the object to be sealed with the gas barrier laminate. While the protective film prevents the gas barrier film from being scratched or cracked during the manufacturing process and the processing and transportation of the sealed body, when the protective film is peeled off at the desired timing, the A gas barrier laminate that does not create a gap between a sealed object and an adhesive layer and can provide good durability of a sealed object, and a method for producing a sealed object using the gas barrier laminate. The purpose is to provide

The present inventors conducted extensive studies based on the above idea of protecting the gas barrier film with a protect film. As a result, a gas barrier laminate having a laminate structure in which an adhesive layer, a gas barrier film, and a protect film are arranged in this order is attached to a glass plate under specific conditions with the adhesive layer as the bonding surface. The above problem 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 protect film to satisfy a specific relationship when I discovered that.

That is, the present invention relates to the following [1] to [14].
[1] A gas barrier laminate having a laminate structure in which an adhesive layer, a gas barrier film, and a protect film are arranged in this order,
The gas barrier laminate is pressed against a glass plate with a roller under the following conditions (α) using the adhesive layer as a bonding surface to attach the gas barrier laminate and the glass plate, and then the following conditions (α) are applied. β), and other conditions are measured in accordance with JIS Z0237:2000, the adhesive force a between the glass plate and the adhesive layer, and the adhesive force between the gas barrier film and the protect film. A gas barrier laminate whose adhesive force b satisfies the following formula (1).
a>b...(1)
Conditions (α): temperature 23°C, pressure 0.2MPa, and speed 0.2m/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 [2] The adhesive layer is a curable adhesive layer. , the gas barrier laminate according to [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 resin (A) includes a modified polyolefin resin (A1).
[5] The curable adhesive layer includes a curable component (B), and the curable component (B) includes a polyfunctional epoxy compound (BL) that is liquid at 25° C. [2] The gas barrier laminate according to any one of [4].
[6] The gas barrier laminate according to [5], wherein the polyfunctional epoxy compound (BL) has a weight average molecular weight (Mw) of 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 layer and a gas barrier layer.
[9] The gas barrier laminate according to [8], wherein the base layer has a resin film containing one or more selected from polycarbonate, cycloolefin polymer, and cycloolefin copolymer as a resin component.
[10] The gas barrier laminate according to [8] or [9], wherein the base 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. laminate.
[14] A method for producing a sealed body, comprising the following steps (1) and (2) in this order.
・Step (1): A step of attaching the gas barrier laminate according to any one of [1] to [13] to an object to be sealed using 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, the process of storing and transporting the gas barrier laminate until it is used, the process of manufacturing a sealed body by sealing an object with the gas barrier laminate, and the process of manufacturing the sealed body While the protective film prevents scratches and cracks on the gas barrier film during processing and transportation, it also prevents damage between the object to be sealed and the adhesive layer when the protective film is peeled off at the desired timing. It becomes possible to provide a gas barrier laminate that does not create gaps and can improve the durability of an object to be sealed, and a method for manufacturing a sealed body using the gas barrier laminate.

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

[Gas barrier laminate]
The gas barrier laminate of the present invention has a laminate structure in which an adhesive layer, a gas barrier film, and a protect film are arranged in this order.
The gas barrier laminate of the present invention is produced by pressing the gas barrier laminate against a glass plate with a roller under the following conditions (α) using the adhesive layer as a bonding surface to bond the gas barrier laminate and the glass plate. After pasting, peel off under the following conditions (β), and other conditions are measured in accordance with JIS Z0237:2000, the adhesive force a between the glass plate and the adhesive layer, the gas barrier film and the protect film The adhesive force b between is adjusted so as to satisfy the following formula (1).
a>b...(1)
Conditions (α): temperature 23°C, pressure 0.2MPa, and speed 0.2m/min
Condition (β): After pasting, 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 present invention, the adhesive between the glass plate and the adhesive layer The force a is measured by peeling off the gas barrier laminate attached to the glass plate from the glass plate. Moreover, 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.
Note that in this specification, the term "gas barrier" refers to a function that prevents the permeation of gases such as oxygen and water vapor.

The gas barrier laminate of the present invention is not particularly limited as long as it has a laminate structure in which an adhesive layer, a gas barrier film, and a protection film are laminated in this order.
The layer structure of the gas barrier laminate according to one embodiment of the present invention includes, for example, the following embodiment in which only an adhesive layer, a gas barrier film, and a protect film are laminated in this order, and furthermore, an optional layer structure in which only an adhesive layer, a gas barrier film, and a protect film are laminated in this order. The following embodiments include a release sheet.
・Adhesive layer/Gas barrier film/Protection film ・Release sheet/Adhesive layer/Gas barrier film/Protection film The mode of the layer structure including the release sheet represents the state before the gas barrier laminate is used as a sealing material. This is what I did. When used as a sealing material, the release sheet is peeled off and removed, and the exposed surface of the adhesive layer and the object to be sealed are bonded together to cover and seal the object. The protection film laminated on the gas barrier film may be removed during the process of sealing the object to be sealed with the gas barrier laminate to produce a sealed body, or during the process of processing or transporting the sealed body. It will be done.

Moreover, the layer structure of the gas barrier laminate of the present invention becomes, for example, the following embodiment after the surface of the exposed adhesive layer and the object to be sealed are bonded together to cover the object to be sealed.
- Adhesive layer/Gas barrier film/Protect film Here, the adhesive layer included in the gas barrier laminate of one embodiment 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 aspect.
- Cured adhesive layer/gas barrier film/protection film In the present invention, the "curable adhesive layer" means an uncured adhesive layer.
In a sealed body produced by sealing an object to be sealed with the gas barrier laminate of the present invention, the gas barrier film is protected by the protect film until the protect film is peeled off, and the gas barrier film is protected from scratches and cracks. occurrence is prevented.
Here, after the protection film is peeled off from the sealing body, the following aspect occurs.
・Adhesive layer/gas barrier film In addition, if the adhesive layer is a curable adhesive layer, after curing the curable adhesive layer and peeling off the protect film from the sealing body, the following It becomes a mode.
- Cured adhesive layer/gas barrier film In this specification, the object to be sealed is sealed by bonding the surface of the exposed adhesive layer and the object to cover the object. is called a "sealed body". In the sealing body, the adhesive layer may be uncured or cured, or may be in an intermediate state between uncured and cured, that is, a semi-cured state.
Note that when the adhesive layer of the sealed body is uncured or in a semi-cured state, the sealed body can also be said to be a "sealing precursor."
Furthermore, in the present invention, the process of processing the sealed body includes a process of curing the adhesive layer of the sealed body.

The present inventors investigated the process of storing and transporting the gas barrier laminate until it is used, the process of manufacturing a sealed body by sealing an object with the gas barrier laminate, and the process of manufacturing the sealed body. In order to prevent the gas barrier film from being scratched or cracked during processing, transportation, etc., we considered protecting the entire surface of the gas barrier film with a protective film and peeling off the protective film at the desired timing.
However, when the protect film is peeled off after the object to be sealed is sealed with a gas barrier laminate, a gap is created between the object to be sealed and the adhesive layer, and oxygen, water vapor, etc. can enter through the gap. It has become clear that there is a risk that the object to be sealed may deteriorate. It has also become clear that the appearance becomes poor.
In order to investigate the cause of this, the present inventors conducted extensive studies. As a result, they found that the force applied when peeling off the protection film causes a gap to occur between the object to be sealed and the adhesive layer.
Therefore, in order to solve the above problem, the present inventors conducted further intensive studies. As a result, when the gas barrier laminate is attached to a glass plate under specific conditions, the adhesive force a between the glass plate and the adhesive layer and the adhesive force b between the gas barrier film and the protect film are as follows: It has been found that the above problem can be solved by making adjustments to satisfy the above formula (1).

Based on this, the present inventors believe that protection can be achieved at any time during the process of sealing an object to be sealed with a gas barrier laminate to produce a sealed body, as well as during the process of processing and transporting the sealed body. It was discovered that even when the film is peeled off, no gap is created between the object to be sealed and the adhesive layer, and it is possible to provide a gas barrier laminate that is extremely easy to use in various processes, and was able to complete the present invention. Ta.

[Physical properties of gas barrier laminate]
The gas barrier laminate of the present invention is produced by pressing the gas barrier laminate against a glass plate with a roller using the adhesive layer as a bonding surface under the following conditions (α) to bond the gas barrier laminate and the glass plate. After that, the adhesive force a between the glass plate and the adhesive layer and the gas barrier film and the protect film were peeled off under the following conditions (β), and other conditions were measured in accordance with JIS Z0237:2000. The adhesive force b between the two is adjusted so as to satisfy the following formula (1).
a>b...(1)
Conditions (α): temperature 23°C, pressure 0.2MPa, and speed 0.2m/min
Condition (β): After pasting, leave it for 24 hours in an environment of 23°C and 50% relative humidity, then peel it 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 greater than the adhesive force b between the gas barrier film and the protect film, preferably 1.0 N/50 mm or more, and more. Preferably it is 2.0 N/50 mm or more, more preferably 3 N/50 mm or more, even more preferably 4 N/50 mm or more, even more preferably 5 N/50 mm or more.
Note that in the gas barrier laminate of one embodiment 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 protect film is smaller than the adhesive force a between the glass plate and the adhesive layer, preferably 1 N/50 mm or less, more preferably It is 0.5 N/50 mm or more, more preferably 0.4 N/50 mm or less, even more preferably 0.3 N/50 mm or less.
Note that in the gas barrier laminate of one embodiment of the present invention, the lower limit of the adhesive force b between the gas barrier film and the protect film is not particularly limited, but is usually 0.05 N/50 mm.

In addition, in the gas barrier laminate of one embodiment 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 protect film is , preferably 0.1 N/50 mm or more, more preferably 0.3 N/50 mm or more, even more preferably 0.7 N/50 mm or more.

Below, regarding the adhesive layer, gas barrier film, and protect film that constitute the laminate structure of the gas barrier laminate of the present invention, the adhesive force a between the glass plate and the adhesive layer and the adhesive force a between the gas barrier film and the protect film will be explained. This will be explained in detail by citing a specific method for satisfying the above equation (1) regarding the adhesive force b.

[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 it satisfies the above formula (1), and includes, for example, a dry-hardening adhesive composition, a heat-melting adhesive composition, and a curable adhesive. adhesive compositions, pressure-sensitive adhesive compositions, etc. 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, an adhesive composition containing a silicone resin, Examples include rubber adhesive compositions, adhesive compositions containing polyolefin resins, and adhesive compositions containing epoxy resins.
These can be used alone or in combination of two or more.
In addition, the adhesive composition may contain a binder resin other than the above-mentioned 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. In addition, 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, and even more preferably is 5 to 80 μm.

In addition, from the viewpoint of ensuring good gas barrier properties, 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, even more preferably 70 g/m ² · day or less.
In addition, in this 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 other general-purpose Measurements using a water vapor permeability measuring device also show similar values.

Here, the adhesive layer included in the gas barrier laminate of one embodiment of the present invention is preferably a curable adhesive layer. Since the adhesive layer is curable, it is in an uncured state at the time of application and can be easily applied to the object to be sealed, as well as having good followability to the unevenness of the object. It can be made into something. Then, by applying the curable adhesive layer to the object to be sealed and then curing it, the object to be sealed and the adhesive layer are firmly adhered. As a result, the gas barrier laminate has excellent performance in preventing deterioration of the object to be sealed due to infiltration of oxygen, water vapor, and the like.
Note that 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 "water vapor permeability of the adhesive layer" described above.
The curable adhesive layer is made of a curable adhesive composition, specifically, for example, a thermosetting adhesive composition that can be cured by heat or energy rays, or an energy ray curable adhesive composition. formed from.
Note that energy rays refer to electromagnetic waves or charged particle beams that have energy quanta, examples of which include ultraviolet rays and electron beams, with ultraviolet rays being preferred.
The curable adhesive layer is preferably a thermosetting adhesive layer formed from a thermosetting adhesive composition.

Here, in one embodiment of the present invention, the curable adhesive layer is formed from an adhesive composition containing the curable component (B). Moreover, from the viewpoint of further improving sealing performance, the curable adhesive layer is more preferably formed of an adhesive composition containing both the polyolefin resin (A) and the curable component (B).

Further, in one embodiment 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). . 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 ( One or more types selected from E) can be mentioned.
In the following explanation, "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 "tackifier (E)" are respectively referred to as "component (A),""component(A')," and "component (B)." , "component (C),""component(D),""component(D')," and "component (E)."

In one aspect of the present invention, the total content of components (A) and (B) in an adhesive composition containing both a polyolefin resin (A) and a curable component (B) is Preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass, based on the total amount (100% by mass) of the active ingredient. It is not less than 100% by mass, and usually not more than 100% by mass.
Further, the adhesive composition may be selected from components (A'), (C), (D), (D'), and (E) in addition to the polyolefin resin (A) and the curable component (B). selected from components (A) and (B), and components (A'), (C), (D), (D'), and (E) in the adhesive composition. The total content of 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 ingredients of the adhesive composition. The content is more preferably 90 to 100% by weight, even more preferably 95 to 100% by weight.
In addition, in this specification, "the active ingredient of an adhesive composition" means the component (solid content) contained in an adhesive composition excluding the dilution solvent.

Components (A), (B), (A'), (C), (D), (D'), and (E) in the adhesive composition will be explained in detail below.

<Polyolefin resin (A)>
In one embodiment of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a polyolefin resin (A).
In this specification, "polyolefin resin" means a polymer having repeating units derived from olefin monomers.
When the adhesive composition contains the polyolefin resin (A), it is easy to reduce the water vapor permeability of the adhesive layer after curing. Therefore, it is easy to improve the water vapor barrier properties 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 within the above range, it is easier to reduce the water vapor permeability of the adhesive layer after curing.
Note that as the content of polyolefin resin (A) in the adhesive composition increases, the adhesive force a between the glass plate and the curable adhesive layer tends to decrease. By adjusting the adhesive force b with the film to a value lower than the adhesive force a, the above formula (1) can be satisfied. In addition, the content of the polyolefin resin (A) in the adhesive composition may be reduced within a range that satisfies the required water vapor barrier properties to reduce the adhesive force a between the glass plate and the curable adhesive layer. The above formula (1) can also be satisfied by adjusting the force to a value higher than the force b.

The olefin monomer contained in the polyolefin 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- Pentene and 1-hexene are preferred.
Note that the polyolefin resin (A) may have units derived from two or more types of α-olefins. Moreover, the polyolefin resin (A) may be a polymer consisting only of repeating units derived from olefin monomers, or may be a polymer composed of repeating units derived from olefin monomers and copolymerized with olefin monomers. It may also be a copolymer consisting of repeating units derived from possible monomers. Examples of the monomer copolymerizable with the olefinic monomer include vinyl acetate, (meth)acrylic acid ester, and styrene.
Note that 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 very 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 elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer , polyisobutylene, polyisoprene, and the like.
These can be used alone or in combination of two or more.

Here, in one embodiment 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 that the polyolefin resin (A1) is included.
In this specification, "modified polyolefin resin (A1)" refers to a polyolefin resin (A) that is a precursor that reacts with a modifier, and the polyolefin resin (A) that is a main chain that has the functionality that the modifier has. It means a polymer in which a group is introduced as a side chain.
Note that the modifier may have two or more types of functional groups in the molecule.

Examples of functional groups possessed by the modifier that can be introduced as side chains into the main chain polyolefin resin (A) include carboxyl groups, groups derived from carboxylic acid anhydrides, and carboxylic acid groups. 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, phosphonic group, nitro group, urethane group, Examples include halogen atoms and alkoxysilyl.
Among these functional groups, carboxyl groups, groups derived from carboxylic acid anhydrides, carboxylic ester groups, hydroxyl groups, ammonium groups, amino groups, imide groups, isocyanates, and alkoxysilyl groups are preferable. Groups derived from the above are preferred.

Here, the modified polyolefin resin (A1) is preferably an acid-modified polyolefin resin from the viewpoint of increasing the reactivity with the curable component (B).
In this specification, "acid-modified polyolefin resin" refers to a precursor polyolefin resin (A) that reacts with a compound having an acid group, so that the main chain polyolefin resin (A) has side acid groups. means a polymer introduced as a chain.
Note that the method and conditions for introducing the acid group of the compound having an acid group as a side chain into the main chain polyolefin resin (A) are not particularly limited, and any 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 main chain polyolefin resin (A), but preferably unsaturated carboxylic acids and their anhydrides are mentioned. .
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, norbornenedicarboxylic 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 preferred from the viewpoint of further improving the sealing performance of the adhesive layer after curing.

Note that 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), Unistol (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), and orevac (registered trademark). (manufactured by ARKEMA), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.

The compounding amount of the compound having an acid group to be reacted with the polyolefin resin (A) as a precursor is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the polyolefin resin (A) as a precursor. , more preferably 0.2 to 3 parts by weight, still more preferably 0.2 to 1.0 parts by weight.
When the amount of the compound having an acid group is within the above range, the sealing performance of the adhesive layer after curing can be easily improved.

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

In one embodiment of the present invention, the polyolefin resin (A) may be composed of only the modified polyolefin resin (A1), or may be composed of the modified polyolefin resin (A1) and an unmodified polyolefin 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, even more preferably 80% by mass, based on the total amount (100% by mass) of the polyolefin resin (A). ~100% by weight, more preferably 90~100% by weight.
When the content of the modified polyolefin resin (A1) is within the above range, it is easier to improve the sealing performance of the adhesive layer after curing.

<Curable component (B)>
In one embodiment of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition contains a curable component (B).
As used herein, "curable component (B)" means a component that forms a network structure and hardens into an insoluble and infusible state by heating, irradiation with energy rays, or the like.
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.
Note that 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 ingredients of the adhesive composition. %, more preferably 5 to 45% by weight, even more preferably 10 to 40% by weight.
When the content of the curable component (B) is within the above range, it is easier to improve the sealing performance of the adhesive layer after curing.
Further, 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 parts by mass. Parts by weight, more preferably 10 to 100 parts by weight. When an adhesive layer formed from an adhesive composition in which the content of the curable component (B) is within this range is cured, the cured adhesive layer has better water vapor barrier properties.

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

Moreover, it is preferable that the curable epoxy resin (B1) contains a polyfunctional epoxy resin (B2).
In this specification, "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 novolac type epoxy resins (e.g. phenol/novolac type epoxy resin, cresol/novolac type epoxy resin, brominated phenol/novolac type epoxy resin); hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Alicyclic epoxy compounds such as glycidyl ether, hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, Aliphatic epoxy compounds such as methylolpropane polyglycidyl ether, 2,2-bis(3-glycidyl-4-glycidyloxyphenyl)propane, and dimethyloltricyclodecane diglycidyl ether; and the like. These bifunctional epoxy resins can 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) that is liquid at 25° C. as component (B).
In the following description, the polyfunctional epoxy compound (BL) that is liquid at 25° C. is also referred to as a "component (BL)."
Component (BL) has the effect of lowering the storage modulus of the adhesive composition (hereinafter also referred to as "storage modulus lowering effect") when the adhesive composition reaches a high temperature. Therefore, in one embodiment of the present invention, when the adhesive composition contains such a component (BL), it is possible to efficiently form an adhesive layer that has excellent followability to irregularities.

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, It is 500 or more, more preferably 1,800 or more, even more preferably 2,100 or more.
Further, from the viewpoint of obtaining an adhesive composition with a further improved storage 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 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 protect film is By adjusting the adhesive force to a value lower than the adhesive force a, the above formula (1) can be satisfied. In addition, the weight average molecular weight (Mw) of the component (BL) is reduced within a range that satisfies the required outgas generation suppression performance, so that the adhesive force a between the glass plate and the curable adhesive layer is lower than the adhesive force b. The above formula (1) can also be satisfied by adjusting to a high value.

The epoxy equivalent of component (BL) is preferably 100 to 1,500 g/eq, more preferably 150 to 1,500 g/eq, even more preferably 200 to 1,400 g/eq, even more preferably 240 to 1,300 g/eq. It is.
As used herein, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of 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 low, the adhesive force 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 protect film to a value lower than the adhesive force a. In addition, 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 higher value than the adhesive force b, the above-mentioned Formula (1) can be satisfied.

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

<Silane coupling agent (C)>
In one embodiment 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, "silane coupling agent (C)" means an organosilicon compound having two or more different reactive groups in the molecule.
When 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. Note that even when the adhesive layer is not curable, the adhesive composition may contain the 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 0.1% by mass, based on the total amount (100% by mass) of the adhesive composition. 09% by mass.
Further, 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). The amount is 0.01 to 5.0 parts by weight, more preferably 0.05 to 1.0 parts by weight.
By having the content of the silane coupling agent (C) within the above range, it is easy to ensure good sealing performance of the adhesive layer after curing even when exposed to a high temperature and high humidity environment for a long time. .

The silane coupling agent (C) should contain at least one alkoxysilyl group in the molecule, from the viewpoint of easily ensuring better sealing performance of the adhesive layer after curing both in normal temperature and high temperature environments. Organosilicon compounds having the following are preferred.
Examples of such silane coupling agents include silicon compounds containing polymerizable unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, - 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 and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3 -Isocyanatepropyltriethoxysilane; and the like. These silane coupling agents can be used alone or in combination of two or more.

<Curing catalyst (D)>
In one embodiment 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)" refers to a catalyst that promotes the reaction of curing the curable component (B) with heat or energy rays.
When the adhesive composition contains the curing catalyst (D), the sealing performance of the cured adhesive layer at high temperatures can be easily improved.
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, based on 100 parts by mass of the curable component (B). It is.
When the content of the curing catalyst (D) is within the above range, it is easier to improve the sealing performance of the cured adhesive layer at high temperatures.

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

<Cationic polymerization initiator (D')>
In one embodiment of the present invention, when the adhesive layer is a curable adhesive layer, it is also preferable that the adhesive composition further contains a cationic polymerization initiator (D'). The cationic polymerization initiator (D') is preferably a thermal cationic polymerization initiator when the adhesive layer is a thermosetting adhesive layer, and the adhesive layer is an energy ray-curable adhesive layer. In this 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, and iodonium salts, with sulfonium salts being preferred. Examples of photocationic polymerization initiators 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 compounds, etc., with sulfonium salt compounds being preferred.
When the adhesive composition contains a cationic polymerization initiator (D'), the curable component (B) is preferably a curable epoxy resin (B1).

<Tackifier (E)>
In one embodiment 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 adhesive properties of the curable adhesive layer, and is an oligomer having a weight average molecular weight (Mw) of usually less than 10,000. It is distinguished from the resin (X) contained in the pressure-sensitive adhesive composition described below. Note that even when the adhesive layer is not curable, the adhesive composition may contain a tackifier (E).
The weight average molecular weight (Mw) of the tackifier (E) is usually less than 10,000, preferably from 400 to 8,000, more preferably from 500 to 5,000, more preferably from 800 to 3,500.

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 the content of the tackifier (E) is preferably reduced. (100% by mass), preferably more than 0% by mass and not more than 30% by mass, more preferably more than 0% by mass and not more than 15% by mass, even more preferably 1 to 10% by mass. Moreover, 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).
Further, the content of the tackifier (E) to be contained in the adhesive composition is preferably more than 0 parts by mass to 80 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of the polyolefin resin (A). The amount is more than 30 parts by weight, more preferably 1 to 20 parts by weight. In addition, 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, and is preferably 0 parts by mass, based on 100 parts by mass of the polyolefin resin (A). It is more preferable.
On the other hand, when the content of the tackifier (E) in the adhesive composition is low, 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 protect film to a lower value. In addition, by increasing the content of the tackifier (E) in the adhesive composition within a range that satisfies the required outgassing suppression performance, the adhesive force a between the glass plate and the curable adhesive layer can be increased. The above formula (1) can also be satisfied by adjusting the adhesive force to a value higher than the adhesive force b.

Examples of the tackifier (E) include rosin resins such as polymerized rosin, polymerized rosin ester, and rosin derivatives; terpene resins such as polyterpene resins, aromatic modified terpene resins and their hydrides, and terpene phenol resins; Indene resin; petroleum resin such as aliphatic petroleum resin, aromatic petroleum resin and its hydride, aliphatic/aromatic copolymer petroleum resin; styrene or substituted styrene polymer; α-methylstyrene homopolymer resin , copolymers of α-methylstyrene and styrene, copolymers of styrenic monomers and aliphatic monomers, copolymers of styrene monomers, α-methylstyrene and aliphatic monomers, and styrene monomers. Styrenic resins such as homopolymers, copolymers of styrene monomers and aromatic monomers; and the like. These tackifiers (E) can be used alone or in combination of two or more.
Among these, as the tackifier (E), styrene resins are preferred, and copolymers of styrene monomers and aliphatic monomers are more preferred.

The softening point of the tackifier (E) is determined from the viewpoint of further improving the shape retention of the formed adhesive layer and enabling the cured adhesive layer to exhibit excellent adhesiveness even in a high temperature environment. Therefore, the temperature is preferably 80°C or higher, more preferably 85 to 170°C, and even more preferably 90 to 150°C.
Note that in this specification, the softening point means a value measured in accordance with JIS K 5902.
When using two or more types of tackifiers (E), it is preferable that the weighted average of the softening points of the tackifiers falls within the above range.

<Other additives>
In one embodiment of the present invention, the adhesive composition may contain other additives other than the above-mentioned components (A) to (E) to the extent that the effects of the present invention are not significantly impaired.
Other additives are selected as appropriate depending on the application, and include, for example, ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, etc. The following additives are mentioned.
These additives can be used alone or in combination of two or more.
Note that even when the adhesive layer is not curable, the adhesive composition may contain these additives.

<Dilution solvent>
In one embodiment of the present invention, the adhesive composition may further contain a diluent solvent from the viewpoint of improving the moldability of the adhesive layer.
The diluent solvent can be appropriately selected from organic solvents; specifically, aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, Examples include ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; and alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane. .
These solvents can be used alone or in combination of two or more.
Note that the content of the solvent is appropriately set in consideration of coating properties and the like.
Moreover, even when the adhesive layer is not curable, the adhesive composition may contain a diluting solvent from the same viewpoint.

<Method for forming adhesive layer>
The method for forming the adhesive layer constituting the gas barrier laminate of the present invention is not particularly limited, and may be appropriately formed by employing known techniques.
Here, in one aspect of the present invention, the adhesive layer is preferably formed from the above adhesive composition. For example, a method may be mentioned in which the above-mentioned adhesive composition is applied on the release-treated surface of the above-mentioned release sheet to form a coating film, and the coating film is dried to form an adhesive layer.
In addition, in this specification, when the adhesive layer is a curable adhesive layer, in the process of forming the curable adhesive layer, the heat treatment using the heat applied when drying the coating film is used to cure the curable adhesive layer. It is not included in the curing process of the adhesive layer.

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

[Gas barrier film]
The gas barrier laminate of the present invention has a gas barrier film. A gas barrier film is laminated onto the adhesive layer. Since the gas barrier laminate of the present invention has a gas barrier film, it can exhibit excellent gas barrier properties that are highly effective in preventing the permeation of gases such as oxygen and water vapor.
Moreover, in the gas barrier laminate of the present invention, a protect film is laminated on a gas barrier film, and the gas barrier film is protected by the protect film. Therefore, in addition to the storage and transportation of the gas barrier laminate until it is used, the process of sealing the object to be sealed with the gas barrier laminate to create a sealed body, and the processing and transportation of the sealed body, etc. During the process, it is possible to prevent the gas barrier film from being scratched or cracked.

In one embodiment of the present invention, the gas barrier film included in the gas barrier laminate preferably has at least a base layer and has a gas barrier function. One embodiment of the gas barrier film includes one having a base layer and a gas barrier layer. For example, an embodiment having the following layer structure may be mentioned.
・Base material layer/gas barrier layer In addition, in the above embodiment of "base material layer/gas barrier layer", in order to increase the adhesion between the base material layer and the gas barrier layer, as in the embodiment below, the base material layer and the gas barrier layer are An anchor coat layer may be provided between the layers.
・Base material layer/anchor coat layer/gas barrier layer

In one embodiment of the present invention, the gas barrier film included in the gas barrier laminate is a single-layer resin film or the like in which the base layer itself has a gas barrier function, and the base layer also functions as a gas barrier layer. Good too.

In one embodiment of the present invention, the gas barrier laminate preferably has a gas barrier layer disposed closer to the adhesive layer than the base material layer, for example, as in the embodiment below.
- Base material layer/gas barrier layer/adhesive layer Since the base material layer is not interposed between the gas barrier layer and the adhesive layer, the performance of the gas barrier laminate in blocking water vapor is further improved.
In addition, when the gas barrier layer is arranged at a position closer to the adhesive layer than the base material layer, the protection film is laminated on the base material layer of the gas barrier film. Since a resin film is used for the base layer as described later, the adhesiveness between the protect film and the base layer tends to increase. In addition, even if the protect film is not directly laminated on the base material layer, if the protect film is laminated via some kind of organic layer provided on the base material layer, the adhesiveness between the protect film and the base material layer will be reduced. tends to increase. However, since the gas barrier laminate of the present invention is adjusted to satisfy the relationship of formula (1) above, when the protective film is peeled off, there is no gap between the object to be sealed and the adhesive layer. Does not occur.

In one aspect of the present invention, the gas barrier film of the gas barrier laminate preferably has a water vapor permeability of 0.1 g/m ² /day or less under an environment of a temperature of 40° C. and 90% RH (relative humidity), More preferably, it is 0.05 g/m ² /day or less, and still more preferably 0.005 g/m ² /day or less.
Since the water vapor permeability of the gas barrier film is 0.1 g/m ² /day or less, deterioration of the object to be sealed can be effectively suppressed by using the gas barrier laminate. For example, it is easy to suppress the intrusion of oxygen, water vapor, etc. into an element such as an organic EL element formed on a transparent substrate, and effectively suppress deterioration of electrodes and organic layers.
Further, also for the gas barrier laminate having a gas barrier film and an adhesive layer, the water vapor permeability in an environment of a temperature of 40° C. and 90% RH (relative humidity) is preferably the same value as above.
In addition, in this specification, "the water vapor permeability of a gas barrier film" means a value measured using a gas permeability measuring device (manufactured by mocon, product name "AQUATRAN 2"), but other general-purpose Measurements using a water vapor permeability measuring device also show similar values.

In one embodiment of the present invention, the gas barrier film included in the gas barrier laminate preferably has optical transparency. Specifically, the total light transmittance measured in accordance with JISK7136:2000 is preferably 80% or higher, more preferably 85% or higher, and even more preferably 90% or higher. . Furthermore, the b* value in the L ^* a ^* b ^* display color system measured in accordance with JISK7136:2000 is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less. It is.

Hereinafter, as a gas barrier film used in the gas barrier laminate of one embodiment 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>
The base material layer included in the gas barrier film is preferably a resin film containing a resin component.
The resin components include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, and cycloolefin. Examples include polymers, cycloolefin copolymers, aromatic polymers, and polyurethane polymers.
Among these, polycarbonate, cycloolefin polymer, and cycloolefin copolymer are preferred from the viewpoint of providing a gas barrier film that is highly transparent and optically isotropic.
In addition, these resins can be used individually or in combination of two or more types. Moreover, the base material layer may be one in which two or more types of resin films are laminated.
Resin films with optical isotropy are preferred as constituent materials for gas barrier films when light emitting devices such as organic EL devices are used in display applications. It has the disadvantage of being prone to cracking.
In the gas barrier laminate of the present invention, even when a resin film that has poor flexibility and is brittle, such as polycarbonate, cycloolefin polymer, or cycloolefin copolymer, is used as the constituent material of the gas barrier film, the gas barrier film Since the gas barrier film is protected by the protection film, it is possible to prevent scratches and cracks from occurring in the gas barrier film during handling, and it is possible to prevent defects such as bright spots from occurring on the display due to the scratches and cracks. Therefore, yield can be improved in display manufacturing processes using light emitting elements such as organic EL elements.

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 still more preferably 5 to 100 μm.
Here, in the gas barrier laminate of the present invention, a protect film is laminated on a gas barrier film. Therefore, even if the base material layer is thin, the thickness of the gas barrier laminate can be ensured by the protection 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 generally makes it difficult to ensure handleability. Therefore, the thickness of the base material layer included in the gas barrier laminate of one embodiment 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 that has undergone a modification treatment, from the viewpoint that the thickness of the gas barrier film can be reduced and it has excellent gas barrier properties. A layer is preferred, and the polymer layer is more preferred. Since the polymer layer is a gas barrier layer, the gas barrier layer can be made highly flexible, and the gas barrier film can have excellent durability against bending.

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, Examples include polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and the like.
These polymer compounds can be used alone or in combination of two or more.
Among these, silicon-containing polymer compounds are preferred, and polysilazane-based compounds are more preferred as the polymer compound contained in the polymer layer, from the viewpoint of being able to form a gas barrier layer with excellent gas barrier properties.
The number average molecular weight of the polysilazane compound is preferably 100 to 50,000.

A 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). It is preferable that

In the above general formula (I), n indicates the number of repeating units and represents an integer of 1 or more.
Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkenyl group represents an aryl group or an alkylsilyl group having a group.
Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.
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, or at least one of Rx, Ry, and Rz is hydrogen. It may also be an organic polysilazane which is a group other than an atom.

The polysilazane compounds can be used alone or in combination of two or more.
Furthermore, as the polysilazane compound, a polysilazane modified product can be used, and a commercially available product can also be used.

In addition to the above-mentioned polymer compound, the polymer layer may further contain other components within a range that does not impair the effects of the present invention.
Other components include, for example, curing agents, other polymers, anti-aging 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% based on the total amount (100% by mass) of the components in the polymer layer, from the viewpoint of providing a gas barrier layer with better gas barrier properties. The amount is preferably 70 to 100% by weight, and even more preferably 80 to 100% by weight.

Further, the thickness of the polymer layer included in 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, a gas barrier laminate having sufficient gas barrier properties can be obtained even if the thickness of the polymer layer is on the order of nanometers.

As a method for forming a polymer layer, for example, a polymer layer forming solution containing at least one polymer compound, optionally other components, and a solvent is coated with a spin coater, knife coater, gravure coater, etc. Examples include a method in which a coating film is formed by coating using a known device, and the coating film is dried.

Examples of the modification treatment of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment. These treatments can be performed alone or in combination of two or more types.
The ion implantation process is a method of modifying the polymer layer by implanting ions into the polymer layer, as will be described later.
Plasma treatment is a method of exposing a polymer layer to plasma to modify the polymer layer. For example, plasma treatment can be performed according to the method described in JP-A-2012-106421.
The ultraviolet irradiation treatment is a method of modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, ultraviolet modification treatment can be performed according to the method described in JP-A-2013-226757.
Among these, ion implantation is a method for modifying the polymer layer from the viewpoint of efficiently modifying the inside of the polymer layer without roughening the surface and forming a gas barrier layer with better gas barrier properties. Treatment is preferred.

Ions injected into the polymer layer during ion implantation include, for example, ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, and fluorine. , ions such as sulfur; ions of alkane gases such as methane and ethane; ions of alkene gases such as ethylene and propylene; ions of alkadiene gases such as pentadiene and butadiene; ions of alkyne gases such as acetylene, etc. 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 organosilicon compounds; etc. can be mentioned.
These ions can be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred from the viewpoint that ions can be more easily implanted and a gas barrier layer having particularly excellent gas barrier properties can be obtained. Argon ions are more preferred.

The method of implanting ions is not particularly limited. Examples include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in the plasma (ions of plasma-generating gas), etc. Since a gas barrier layer can be easily obtained, A method of implanting ions is preferred.
A method for implanting ions in plasma is, for example, generating plasma in an atmosphere containing a plasma generating gas and applying a negative high voltage pulse to a layer into which ions are to be implanted. This can be done by implanting ions into the surface of the layer to be implanted.

Examples of the inorganic film used as the gas barrier layer include films formed by vapor phase deposition of inorganic compounds and metals. Raw materials for inorganic compound films include 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; Examples include sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxycarbides; inorganic nitride carbides; and inorganic oxynitride carbides.
Examples of raw materials for the metal film include aluminum, magnesium, zinc, and tin.
These can be used alone or in combination of two or more.
Among these, from the viewpoint of gas barrier properties, inorganic films made from inorganic oxides, inorganic nitrides, or metals are preferable, and from the viewpoint of transparency, inorganic films made from inorganic oxides or inorganic nitrides are preferable. is preferred. 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, even more preferably 40 to 200 nm, from the viewpoint of gas barrier properties and handleability.

Vapor-phase film formation methods for forming inorganic films include PVD (physical vapor deposition) methods such as vacuum evaporation, sputtering, and ion plating, and CVD such as thermal CVD, plasma CVD, and photoCVD. method (chemical vapor deposition method).

<Anchor coat layer>
In one embodiment of the present invention, an anchor coat layer may be provided between the base layer and the gas barrier layer in order to further improve the adhesion between the base 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 protection film. The protect film is laminated on the gas barrier film to protect the gas barrier film.
In addition, even if the protect film is peeled off at the desired timing, such as when the protection of the gas barrier film is no longer necessary or when it is necessary to expose the gas barrier film, there may be a gap between the object to be sealed and the adhesive layer. This prevents the intrusion of oxygen, moisture, etc. Moreover, poor appearance is also prevented.

In one embodiment of the present invention, the protect film included in the gas barrier laminate has at least a protect layer. Although the protection film may have a single layer structure, it is preferably a laminate structure of a protection layer and an adhesive layer. By having a laminated structure of a protect layer and an adhesive layer, it is easy to adjust the adhesive strength of the protect film and obtain a gas barrier laminate that satisfies the above formula (1).

In addition, the gas barrier laminate of the present invention has a protect film, so that the base material layer of the gas barrier film can be made thin and the handling properties of the gas barrier laminate can be made good.
In one embodiment of the present invention, the total thickness of the protect film and the base layer of the gas barrier film is preferably 40 to 500 μm, more preferably 40 to 200 μm, and still more preferably 50 to 150 μm.

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

<Protect layer>
As the protect layer of the protect 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 layer of the gas barrier film. Such resin components include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, and aromatic resin. Examples include polymers, polyurethane polymers, and the like.
In addition, these resins can be used individually or in combination of two or more types. Furthermore, colored films of these may also be used. By coloring, it is possible to easily determine the presence or absence of a protection film, and the interface between the gas barrier film and the protection film can be easily recognized, which is convenient when peeling off the protection film.

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

The ratio of the thickness of the protect layer of the protect film to the thickness of the base material layer of the gas barrier film (protect layer thickness/base material layer thickness) is such that the thickness of the gas barrier laminate can be adjusted even when the base material layer is thinned. From the viewpoint of improving handling properties, 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 that the protection film has is a layer that is laminated on one side of the protection layer and is used to bond the protection 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 protect film is preferably adjusted to be low from the viewpoint of satisfying the relationship of the above formula (1).
The adhesive force b between the gas barrier film and the protection film can be adjusted to be low by lowering the adhesiveness of the adhesive layer of the protection film.
Examples of methods for reducing the tackiness of the adhesive layer of the protection film include reducing the thickness of the adhesive layer and changing the type of adhesive layer. Note that the adhesive layer included in the gas barrier laminate of the present invention must have properties necessary for sealing the object to be sealed. Therefore, rather than changing the adhesive force a by adjusting the type of raw material or the amount of raw materials in the adhesive composition for forming the adhesive layer, it is sufficient to control only the adhesion characteristics of the adhesive layer to the gas barrier film. It is easier to change the adhesive force b by adjusting the adhesiveness of the adhesive.

The thickness of the adhesive layer is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 40 μm, and even more preferably 1 μm to 25 μm, from the viewpoint of reducing the adhesiveness of the adhesive layer.

The type of adhesive layer can be changed by selecting the resin that is a polymer contained in the adhesive composition for forming the adhesive layer. Hereinafter, the adhesive composition for forming the adhesive layer will be explained, also taking into consideration the selection of the polymer resin.

<Adhesive composition>
The adhesive composition that is the material for forming the adhesive layer contains resin (X), which is a polymer.
The resin (X) itself may or may not have adhesive properties. When the resin (X) does not have tackiness, the tackifier described below can be added to the tackifier composition so that the tackifier layer formed from the tackifier composition exhibits tackiness. Good too.
In addition, in one aspect of the present invention, components other than the resin (X) contained in the adhesive composition can be adjusted as necessary.
For example, in one embodiment of the present invention, from the viewpoint of adjusting the adhesive strength to a desired range, the adhesive composition may further contain one or more selected from the group consisting of a tackifier and a crosslinking agent, In addition to these, it may contain one or more selected from the group consisting of diluent solvents and adhesive additives used in general adhesives.

(Resin (X))
The weight average molecular weight (Mw) of the resin (X) is preferably 10,000 or more, more preferably 10,000 to 2,000,000, and still more preferably 20,000 to 1,500,000.
Examples of the resin (X) contained in the adhesive composition include acrylic resins, urethane resins, olefin resins, acrylic urethane resins, and polyester resins.
These resins (X) can be used alone or in combination of two or more.
In addition, when these resins (X) are copolymers having two or more types of structural units, the form of the copolymer is not particularly limited, and may include block copolymers, random copolymers, and graft copolymers. It may be any copolymer.
Here, from the viewpoint of appropriately adjusting the adhesiveness of the adhesive layer formed by the adhesive composition and adjusting the adhesive force b between the gas barrier film and the protect film to be low, the resin (X) is an acrylic resin. olefin resins are preferred, and acrylic resins are more preferred.

The content of resin (X) in the 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 adhesive composition. %, more preferably 50 to 99.90% by weight, still more preferably 55 to 99.80% by weight, even more preferably 60 to 99.50% by weight.
Hereinafter, in one embodiment of the present invention, preferred acrylic resins and olefin resins as resin (X) will be described.

(acrylic resin)
In one embodiment of the present invention, from the viewpoint of appropriately adjusting the adhesiveness of the adhesive layer formed by the adhesive composition and adjusting the adhesive force b between the gas barrier film and the protect film to be low, the adhesive composition It is preferable that the resin (X) contained in the product contains an acrylic resin.
The content 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 adhesive composition. %, more preferably 70 to 100% by weight, even more preferably 85 to 100% by weight.

Examples of acrylic resins that can be used as the resin (X) include polymers containing structural units derived from alkyl (meth)acrylates having a linear or branched alkyl group, and (meth)acrylates having a cyclic structure. Examples include polymers containing structural units derived from the above.

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. More preferred is an acrylic copolymer (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).

The number of carbon atoms in the alkyl group of 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 a lower level as the adhesive layer becomes thinner. .
In addition, the alkyl group that the monomer (a1') has 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, tridecyl ( Examples include meth)acrylate, stearyl (meth)acrylate, and the like.
As the monomer (a1'), methyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are more preferred.
These monomers (a1') can be used alone or in combination of two or more.
Among these, it is preferable to use a combination of butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate as the monomer (a1').
In addition, the mass ratio of these [butyl (meth)acrylate/2-ethylhexyl (meth)acrylate] is preferably from 1/9 to 1/9 from the viewpoint of easily adjusting the adhesive force b between the gas barrier film and the protect film to be low. The ratio is 5/5, more preferably 1/9 to 4/6, 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 100% by mass, based on the total structural units (100% by mass) of the acrylic polymer (A0) or acrylic copolymer (A1). The content is 99.9% by weight, more preferably 70 to 99.5% by weight, even more preferably 80 to 99.0% by weight.

The functional group that the monomer (a2') has refers to a functional group that reacts with a crosslinking agent that may be contained in the pressure-sensitive adhesive composition described below and can serve as a crosslinking starting point, or a functional group that has a crosslinking promoting effect, such as a hydroxyl group, Examples include carboxyl group, amino group, and epoxy group.
That is, examples of the monomer (a2') include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.
These monomers (a2') can be used alone or in combination of two or more.
As the monomer (a2'), hydroxyl group-containing monomers and carboxyl group-containing monomers are preferred.

Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate. ) acrylate, hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.

Carboxy group-containing monomers include, for example, 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.
As the monomer (a2'), 2-hydroxyethyl (meth)acrylate is preferred.
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). More preferably 0.5 to 20% by weight, even more preferably 0.7 to 10% by weight. The higher the content of the structural unit (a2) serving as a crosslinking starting point, the lower the adhesive force b between the gas barrier film and the protect film tends to be.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').
In addition, in the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is preferably 70 to 100% of the total structural units (100% by mass) of the acrylic copolymer (A1). % by mass, more preferably 80 to 100% by mass, even more preferably 85 to 100% by mass, 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; Having a cyclic structure such as benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, imido (meth)acrylate, etc. (Meth)acrylate; Examples include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, N-vinylpyrrolidone, and the like.
These monomers (a3') can be used alone or in combination of two or more.
As the monomer (a3'), vinyl acetate is preferred.

(olefin resin)
The olefin 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 resins can be used alone or in combination of two or more.
Specific olefin resins include, for example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other α- Copolymers with olefins, copolymers with propylene and other α-olefins, copolymers with ethylene and propylene with other α-olefins, copolymers with ethylene and other ethylenically unsaturated monomers. Examples include polymers (ethylene-vinyl acetate copolymer, ethylene-alkyl (meth)acrylate copolymer, ethylene-vinyl alcohol copolymer, etc.). Among these, ethylene-vinyl acetate copolymers, which are copolymers of ethylene and other ethylenically unsaturated monomers, are preferred.
In addition, examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc. It will be done.
Examples of the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth)acrylate, and vinyl alcohol.

The olefin resin may be a rubber resin. Examples of rubber-based resins that can be used as resin (X) include polyisobutylene-based resins. The polyisobutylene resin (hereinafter also referred to as "PIB resin") is not particularly limited as long as it has a polyisobutylene skeleton in at least one of the main chain and side chain.
The number average molecular weight (Mn) of the PIB 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 PIB resins include polyisobutylene which is a homopolymer of isobutylene, copolymers of isobutylene and isoprene, copolymers of isobutylene and n-butene, copolymers of isobutylene and butadiene, and copolymers of these. Examples include brominated or chlorinated halogenated butyl rubber. Among these, copolymers of isobutylene and isoprene are preferred.

In addition, when the PIB-based resin is a copolymer, it is assumed that the structural unit consisting of isobutylene is contained the most among all the structural units.
The content of the structural unit consisting of isobutylene is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol% of the total structural units (100 mol%) of the PIB resin. be.
These PIB resins can be used alone or in combination of two or more.

Further, when using a PIB resin, it is preferable to use a rubber resin capable of a crosslinking reaction, such as polyisoprene rubber having a carboxylic acid functional group.

(Crosslinking agent)
In one aspect of the present invention, the pressure-sensitive adhesive composition comprises an acrylic copolymer having the aforementioned structural units (a1) and (a2), a resin ( ), it is preferable to further contain a crosslinking agent.
The crosslinking agent reacts with the functional group of the resin (X) to crosslink the resins. The adhesive force b between the gas barrier film and the protect film can be adjusted depending on the degree of crosslinking between the resins.

Examples of the crosslinking agent include isocyanate crosslinking agents such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and adducts thereof; ethylene glycol glycidyl ether, 1,3-bis(N,N-diglycidyl-amino); Epoxy crosslinking agents such as methyl)cyclohexane; aziridine crosslinking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; chelate crosslinking agents such as aluminum chelate; and the like.
These crosslinking agents can be used alone or in combination of two or more.
Among these crosslinking agents, isocyanate-based crosslinking agents are preferred from the viewpoint of making it easier to adjust the adhesive force to a lower level as the adhesive layer becomes thinner, and from the viewpoint of ease of acquisition.

The content of the crosslinking agent is appropriately adjusted depending on the number of functional groups that the resin (X) has, but for example, 100 parts by mass of the resin (X) having the above-mentioned functional groups such as the acrylic copolymer. The amount is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 7 parts by weight, and even more preferably 0.05 to 4 parts by weight. When the content of the crosslinking agent is high and the crosslinking density in the adhesive layer is high, the adhesive force b between the gas barrier film and the protect film tends to be low.

(Tackifier)
In one embodiment of the present invention, the adhesive composition may further contain a tackifier together with the resin (X).
The same tackifier as the above-mentioned tackifier (E) can be used as the tackifier.
The content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, even more preferably 0.1 to 50% by mass, based on the total amount of the adhesive composition. More preferably 0.5 to 45% by weight, even more preferably 1.0 to 40% by weight.

(Additive for adhesives)
In one aspect of the present invention, the pressure-sensitive adhesive composition contains additives for pressure-sensitive adhesives used in general pressure-sensitive adhesives other than the above-mentioned tackifier and crosslinking agent, to the extent that the effects of the present invention are not impaired. You can leave it there.
Examples of the adhesive additives include antioxidants, softeners (plasticizers), rust preventives, retarders, catalysts, ultraviolet absorbers, reaction accelerators, and reaction inhibitors.
Note that these adhesive additives can be used alone or in combination of two or more.
When these adhesive additives are contained, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.0001 to 20 parts by mass, based on 100 parts by mass of resin (X). is 0.001 to 10 parts by mass.

(dilution solvent)
In one aspect of the present invention, the adhesive composition may contain water or an organic solvent as a diluting solvent in addition to the various active ingredients described above, and may be in the form of a solution.
Examples of organic solvents 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. etc.
Note that these diluting solvents can be used alone or in combination of two or more.

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

[Release sheet]
As the release sheet, conventionally known release sheets can be used. For example, a release sheet having a release layer treated with a release agent on a base material for release sheets may be mentioned.
Examples of base materials for release sheets include paper bases such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating thermoplastic resin such as polyethylene on these paper bases; polyethylene terephthalate resin, polybutylene terephthalate resin. , a plastic film formed from polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc.
These can be used alone or in combination of two or more. Moreover, the base material for a release sheet may be a laminate obtained by laminating two or more of these.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long-chain alkyl resins, alkyd resins, and fluororesins.
These can be used alone or in combination of two or more.

[Method for manufacturing gas barrier laminate]
The method for producing the gas barrier laminate is not particularly limited.
For example, in the method for manufacturing an adhesive layer described above, a gas barrier film is attached to the surface of the adhesive layer that is not provided with a release sheet, and the adhesive layer of the protect film and the gas barrier film are bonded together. A flexible laminate can be produced.
When the protect film is a single layer protect layer, a gas barrier laminate can be manufactured by bonding the protect layer and the gas barrier film. For example, a protective layer can be laminated on a gas barrier film due to the self-adhesive properties of the protective film.

[Sealing body]
The sealed body is obtained by sealing an object to be sealed by bonding the surface of the exposed adhesive layer and the object to cover the object.
Examples of the object to be sealed include electronic devices such as organic EL elements, organic EL display elements, liquid crystal display elements, and solar cell elements.

Here, the object to be sealed may be mounted on a substrate such as a transparent substrate.
When the object to be sealed is mounted on a substrate such as a transparent substrate, the curable adhesive layer of the gas barrier laminate coats the surface of the object and the surface of the substrate around the object. It is attached to cover.
The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material with high visible light transmittance. Further, it is preferable to use a material that has high blocking performance for blocking water vapor or gas that attempts to enter from the outside of the element, and has excellent solvent resistance and weather resistance.
Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, Examples include transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins.
The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and ability to block the inside and outside of the element.

[Method for manufacturing sealed body]
The method for manufacturing the sealed body is not particularly limited. For example, a sealed body can be obtained by covering at least the surface of an object to be sealed with an adhesive layer of a gas barrier laminate. When the adhesive layer of the gas barrier laminate is a curable adhesive layer, the adhesive layer of the gas barrier laminate can be cured by performing a curing treatment such as heating or energy ray irradiation. Adhesion to the surface of the sealant can be improved. The process of peeling and removing the protective film from the gas barrier laminate is a step in the process of sealing the object to be sealed with the gas barrier laminate to produce a sealed body, and the 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 created between the object to be sealed and the adhesive layer even if the protection film is peeled from the gas barrier laminate at any timing. Therefore, deterioration of the object to be sealed due to infiltration of moisture, oxygen, etc. is prevented.
That is, in one embodiment of the present invention, the method for manufacturing a sealed body preferably 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 using the adhesive layer as a bonding surface. ・Step (2): A step of peeling the 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 may be performed before or after the adhesive layer is cured. There may be.
When curing the adhesive layer by heating, the protect film has gas barrier properties to prevent defects due to changes in the properties and shape of the protect layer and adhesive layer of the protect film due to the heat during curing of the adhesive layer. The step of peeling and removing from the laminate is preferably performed before the adhesive layer is cured.
In addition, even when the adhesive layer is cured by energy ray irradiation, from the viewpoint of suppressing the reduction in the amount of energy rays irradiated to the adhesive layer due to the protect layer and adhesive layer of the protect film, the protect film has gas barrier properties. The step of peeling and removing from the laminate is preferably performed before the adhesive layer is cured.
That is, in one embodiment of the present invention, the method for manufacturing a sealed body preferably 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 using the curable adhesive layer as a bonding surface. ・Step (2): Peeling the protective film from the gas barrier laminate. Step (3): Curing the curable adhesive layer The curing treatment in step (3) may be performed by heating or by irradiation with energy rays.
The gas barrier laminate of the present invention is designed such that 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 protect film satisfy the above formula (1). Even before the adhesive layer is cured, the protection film can be peeled off without creating a gap between the object to be sealed and the adhesive layer.

The conditions for bonding the adhesive layer of the gas barrier laminate and the object to be sealed are not particularly limited. The temperature during application is, for example, 10 to 60°C, preferably 20 to 45°C. This bonding process may be performed while applying pressure. When the adhesive layer included in 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 (1 to 6 hours).
When the adhesive layer included in 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 mW/cm 2 . -1000 seconds, preferably 1-500 seconds.

The present invention will be specifically explained 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 It was measured using a film thickness measuring device (manufactured by Filmetrics Co., Ltd., product name "F20").
(2) Thickness of gas barrier layer Measured using a spectroscopic ellipsometer (manufactured by JA Woollam Japan Co., Ltd., product name "M-2000").
(3) Measurement of the thickness of each layer other than the anchor coat layer and gas barrier layer Using a constant pressure thickness measuring device manufactured by Techlock Co., Ltd. (model number: "PG-02J", standard specifications: JIS K6783, Z1702, Z1709 compliant) It was measured using

[Weight average molecular weight (Mw)]
Weight average molecular weight (Mw) of the modified polyolefin resin (A1) used as the polyolefin resin (A), which is a raw material for the curable adhesive layer, and the polyfunctional epoxy compound (B2) used as the curable component (B) The weight average molecular weight (Mw) of , the weight average molecular weight (Mw) of the acrylic resin that is the raw material for the adhesive layer of the protect film, and the number average molecular weight (Mn) of the PIB resin are values measured by the following method. It 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 using a gel permeation chromatography (GPC) device (manufactured by Tosoh Corporation, product name "HLC-8320") under the following conditions, and using the values converted to the weight average molecular weight and number average molecular weight of standard polystyrene. there was.
(Measurement condition)
・Measurement sample: Tetrahydrofuran solution with a sample concentration of 1% by mass ・Column: 2 “TSK gel Super HM-H” and 1 “TSK gel Super H2000” (both manufactured by Tosoh Corporation) connected in sequence・Column temperature: 40℃
・Developing solvent: Tetrahydrofuran ・Flow rate: 0.60mL/min

(2) Weight average molecular weight (Mw) of polyfunctional epoxy compound (B2)
The weight average of the standard polystyrene corresponding to the retention time of the peak with the largest area among the multiple observed peaks measured under the above conditions using the above gel permeation chromatograph (GPC) device. The value was converted to molecular weight.

[Production of gas barrier laminate]
A gas barrier film, a curable adhesive layer, and a protect film described below were prepared and laminated to produce 18 types of gas barrier laminates 1 to 18.

(1) Production of gas barrier film Polyethylene terephthalate (manufactured by Toray Industries, Inc., PET50A4100, thickness: 50 μm) is used as a base layer, and one side of the base layer (smooth side that is not treated for easy adhesion) 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 Mayer 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 was irradiated with UV under the following conditions to cure the coating film, and an anchor with a thickness of 1 μm was used. A coat layer was formed.
(UV irradiation conditions)
・UV lamp: High pressure mercury lamp ・Line speed: 20m/min ・Total light amount: 120mJ/cm ²
・Illuminance: 200mW/ ^cm2
・Lamp height: 104mm

Next, a coating material mainly composed of perhydropolysilazane (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, a gas barrier layer was formed by plasma ion implantation of argon (Ar) into the surface of the polysilazane layer using a plasma ion implantation device, and a gas barrier film 1 having the following laminated structure was produced.
(Laminated structure of gas barrier film 1)
・Base material layer/anchor coat layer/gas barrier layer

(2) Formation of adhesive layer Three types of thermosetting adhesive layers 1 to 3 described below were formed as adhesive layers.

(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 part by mass of silane coupling agent (C), curing catalyst Adhesive composition 1 having a solid content concentration of 20% by mass was prepared by dissolving 0.6 parts by mass of (D) in methyl ethyl ketone.
Polyolefin resin (A), thermosetting component (B-1) used as curable component (B), silane coupling agent (C), and curing catalyst (D) used in the preparation of adhesive composition 1. ) is shown below.
・Polyolefin resin (A): Manufactured by Mitsui Chemicals, product name "Unistol H-200", acid-modified α-olefin polymer, solid at 25°C, weight average molecular weight (Mw) = 52,000, modified polyolefin This resin corresponds to the type 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) = This compound corresponds to a polyfunctional epoxy compound (BL) that is liquid at 3,200°C 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 Kasei Kogyo Co., Ltd., product name "Curezol 2E4MZ"

The prepared adhesive composition 1 was applied onto the release-treated surface of a release sheet (manufactured by Lintec Corporation, product name "SP-PET381031"), and the resulting coating film was heated at 100°C for 2 minutes to determine the thickness. A thermosetting adhesive layer 1 having a thickness of 10 μm was formed.

(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 as shown below. Adhesive composition 2 was prepared by changing the thermosetting component (B-2) to form a thermosetting adhesive layer 2.
・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) = This compound corresponds to a polyfunctional epoxy compound (BL) that is liquid at 1,400°C 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 part by mass of silane coupling agent (C), curing catalyst Adhesive composition 3 having a solid content concentration of 28% by mass was prepared by dissolving 1.2 parts by mass of (D) and 50 parts by mass of tackifier (E) in methyl ethyl ketone.
The polyolefin resin (A), silane coupling agent (C), and 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 "(2-2) Formation of thermosetting adhesive layer 2" above.
The tackifier (E) was a copolymer of a styrene monomer and an aliphatic monomer (manufactured by Mitsui Chemicals, Inc., product name "FTR6100", softening point = 95°C).
Otherwise, the thermosetting adhesive layer 3 was formed using the same method as in "(2-1) Formation of the thermosetting adhesive layer 1" above.

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

(3-1) Preparation of Protect Film 1 A polyethylene film (manufactured by San-A Kaken Co., Ltd., product name "PAC-3-70") was used as Protect Film 1.
(Configuration of protective film 1)
・Adhesive layer (ethylene-vinyl alcohol copolymer)/protection layer (low-density polyethylene film)

(3-2) Preparation of protection film 2 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 were copolymerized to form a (meth)acrylic 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 crosslinking agent (hexamethylene diisocyanate), and 0.010 parts by mass of a reaction accelerator (dioctyltin dilaurate) were reacted. The mixture was mixed with 1.0 parts by mass of an inhibitor (acetylacetone), thoroughly stirred, and diluted with methyl ethyl ketone to obtain a pressure-sensitive adhesive composition having a solid content concentration of 37% by mass.
The adhesive composition was applied with a knife onto the release-treated surface of a release sheet (manufactured by Lintec Corporation, product name: "SP-PET381031", thickness: 38 μm), in which one side of a polyethylene terephthalate film was treated with a silicone release agent. A coating film was formed by coating with a coater. The coating film was heat-treated at 90° C. for 1 minute to form an adhesive layer with a thickness of 20 μm. Thereby, a laminate consisting of an adhesive layer and a release sheet was obtained.
Next, the adhesive layer of the laminate was bonded to 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). By doing so, a protect film 2 having the following laminated structure was produced.
(Configuration of protective film 2)
・Release sheet/adhesive layer (thickness: 20μm, acrylic resin)/protection layer (thickness: 38μm, polyethylene terephthalate film)

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

(3-4) Preparation of protection film 4 Isobutylene and isoprene copolymer (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 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 family petroleum resin (manufactured by Nippon Zeon Co., Ltd., product name "Quinton A100", softening point 100 ° C.) and 1 mass of crosslinking agent (manufactured by Mitsubishi Chemical Corporation, product name "TC-5", epoxy compound) Part was dissolved in toluene to obtain an adhesive composition having a solid content concentration of 25% by mass.
A protect film 4 was produced in the same manner as in "(2) Protect film 2" above, except that the pressure-sensitive adhesive composition was used and the thickness of the pressure-sensitive adhesive layer was adjusted to 2 μm.
(Configuration of protective film 4)
・Release sheet/adhesive layer (thickness: 2μm, PIB resin)/protection layer (thickness: 38μm, polyethylene terephthalate film)

(3-5) Preparation of Protect Film 5 The thickness of the adhesive layer of Protect Film 4 was changed to 10 μm, and Protect Film 5 was produced.
(Configuration of protective film 5)
・Release sheet/adhesive layer (thickness: 10μm, PIB resin)/protection layer (thickness: 38μm, 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 protect film 6.
(Configuration of protective film 6)
・Adhesive layer (acrylic resin)/protection layer (polyethylene terephthalate film)

(4) Production of gas barrier laminate The gas barrier layer of the gas barrier film 1 produced in "(1) Production of gas barrier film" above and the thermosetting adhesive formed in "(2) Formation of adhesive layer" above Agent layers 1 to 3 were bonded to each other. Then, on the barrier film side (surface of the base material layer), the protective film 1 to 6 are laminated with the adhesive layer as the bonding surface, and gas barrier film 1, thermosetting adhesive layers 1 to 3, and protection films 1 to 6 are laminated in the combinations shown in Table 1. Bodies 1 to 18 were produced.

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

(1) Measurement of adhesive strength b of the protect film to the gas barrier film Peel off the release sheet of the gas barrier laminate cut into 50 mm width and 20 mm length, and use the thermosetting adhesive layer as the bonding surface to attach the soda lime glass plate. A gas barrier laminate was laminated on the top. For lamination, a laminating device equipped with rollers (roll-type multi-laminator manufactured by Japan Office Laminator Co., Ltd.) was used, 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 lamination, 50% R.I. at 23°C. H. (relative humidity) for 24 hours, and under the same environment, peel off the protective film from the gas barrier film at a peeling angle of 180°, and perform a 180° peel adhesive force measurement test (N/50mm, The adhesive force b between the gas barrier film and the protect film was measured at a peeling rate of 300 mm/min. In addition, in the appearance evaluation described below, if any lifting occurred, the thermosetting adhesive layer of the gas barrier laminate was pasted on a soda lime glass plate via double-sided tape and measured again, and the adhesive force b was measured. It was measured.

(2) Appearance evaluation When measuring the adhesive force b between the gas barrier film and the protect film, check whether any lifting is observed between the soda lime glass plate that is the adherend and the thermosetting adhesive layer. Confirmed visually. The case where no lifting was observed was rated as "A", and the case where lifting occurred was rated as "F".

(3) Measurement of adhesive force a between glass plate and thermosetting adhesive layer Peel off the release sheet of the gas barrier laminate cut into 50 mm width and 20 mm length, and paste the thermosetting adhesive layer. A gas barrier laminate was laminated onto a soda lime glass plate as a mating surface. For lamination, a laminating device equipped with rollers (roll-type multi-laminator manufactured by Japan Office Laminator Co., Ltd.) was used, 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 lamination, 50% R. H. (relative humidity) for 24 hours, and under the same environment, the gas barrier laminate was peeled off from the soda lime glass plate at a peeling angle of 180°, and a 180° peeling adhesion measurement test ( N/50 mm, peeling speed: 300 mm/min), 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 have no lifting and have a good appearance.
On the other hand, as in Comparative Examples 1 to 3, in the gas barrier laminates where a<b, lifting was observed and the appearance was poor.

Claims (16)

A gas barrier laminate having a laminate structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order,
The protection film has a protection layer and an adhesive layer, and the adhesive layer is attached to the gas barrier film,
The adhesive layer is a layer formed from an adhesive composition containing a polyolefin resin (A),
The gas barrier laminate is pressed against a glass plate with a roller under the following conditions (α) using the adhesive layer as a bonding surface to attach the gas barrier laminate and the glass plate, and then the following conditions (α) are applied. β), and other conditions are measured in accordance with JIS Z0237:2000, the adhesive force a between the glass plate and the adhesive layer, and the adhesive force between the gas barrier film and the protect film. A gas barrier laminate whose adhesive force b satisfies the following formula (1).
a>b...(1)
Conditions (α): temperature 23°C, pressure 0.2MPa, and speed 0.2m/min
Condition (β): After pasting, leave it for 24 hours in an environment of 23°C and 50% relative humidity, then peel it 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 1 , wherein the polyolefin resin (A) includes a modified polyolefin resin (A1). Any one of claims 2 to 3 , 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 4 , 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 4 , 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 6 , wherein the gas barrier film has a base layer and a gas barrier layer. The gas barrier laminate according to claim 7 , wherein the base material layer has a resin film containing one or more selected from polycarbonate, cycloolefin polymer, and cycloolefin copolymer as a resin component. The gas barrier laminate according to claim 7 or 8 , wherein the base layer has a thickness of 30 μm or less. The gas barrier laminate according to any one of claims 7 to 9 , 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 7 to 10 , wherein the gas barrier layer and the adhesive layer are directly laminated. A gas barrier laminate having a laminate structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order,
The protection film has a protection layer and an adhesive layer, and the adhesive layer is attached to the gas barrier film,
The gas barrier film has a base layer and a gas barrier layer,
The base layer has a resin film containing one or more selected from polycarbonate, cycloolefin polymer, and cycloolefin copolymer as a resin component,
The gas barrier laminate is pressed against a glass plate with a roller under the following conditions (α) using the adhesive layer as a bonding surface to attach the gas barrier laminate and the glass plate, and then the following conditions (α) are applied. β), and other conditions are measured in accordance with JIS Z0237:2000, the adhesive force a between the glass plate and the adhesive layer, and the adhesive force between the gas barrier film and the protect film. A gas barrier laminate whose adhesive force b satisfies the following formula (1).
a>b...(1)
Conditions (α): temperature 23°C, pressure 0.2MPa, and speed 0.2m/min
Condition (β): After pasting, leave it for 24 hours in an environment of 23°C and 50% relative humidity, then peel it off at a peeling speed of 300 mm/min. The gas barrier laminate according to claim 12 , wherein the base layer has a thickness of 30 μm or less. The gas barrier laminate according to claim 12 or 13 , 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 12 to 14 , wherein the gas barrier layer and the adhesive layer are directly laminated. A method for manufacturing a sealed body, comprising the following steps (1) and (2) in this order.
・Step (1): A step of attaching the gas barrier laminate according to any one of claims 1 to 15 to an object to be sealed using the adhesive layer as a bonding surface. ・Step (2): Applying a protective film. Step of peeling from the gas barrier laminate