TWI805854B - gas barrier laminate - Google Patents

Abstract

A gas barrier laminate comprising a laminated structure in which a curable adhesive layer, a gas barrier film, and a protective film are sequentially arranged, wherein the curable adhesive layer is used as a bonding surface, and the gas barrier layer is rolled onto a roll. The laminate is pressed against the glass plate under the following condition (α), and after the above-mentioned gas-barrier laminate is attached to the above-mentioned glass plate, it is peeled off under the following condition (β). Other conditions follow JIS Z0237:2000 to measure the above-mentioned glass The adhesive force a between the board and the adhesive layer, and the adhesive force b between the gas barrier film and the protective film, the adhesive force a and the adhesive force b satisfy the following formula (1), a＞b･･･(1) Condition (α): temperature 23°C, pressure 0.2 MPa and speed 0.2 m/min, Condition (β): After sticking, let it stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and peel it off at a peeling speed of 300 mm/min.

Description

gas barrier laminate

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 light with high luminance by low-voltage DC driving. However, organic EL elements have a problem that light emission characteristics tend to decrease over time. This problem is considered to be caused by the penetration of oxygen, moisture, etc. into the interior of the organic EL element to degrade the electrodes or organic layers. Therefore, as a measure against this problem, sealing of the organic EL element with a sealing material to prevent infiltration of oxygen, moisture, and the like has been performed. Specifically, a method of sealing an object to be sealed, such as an organic EL element, using a gas-barrier sealing material having a layered structure is proposed. Patent Document 1 describes a technique for sealing an organic EL element with a sealing film laminated on an adhesive film with a gas barrier film. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-197517

[Outline of Invention] [Problems to be Solved by the Invention]

Objects to be sealed that need to be prevented from deteriorating due to oxygen, moisture, etc., such as electronic devices such as organic EL elements, can be sealed with a gas-barrier laminate having a laminated structure of an adhesive layer and a gas-barrier film, as shown in patent documents The sealing film described in 1 has a layer structure for sealing.

In addition, in the processes up to storage and transportation of the gas-barrier laminated body, the process of sealing the object to be sealed with the gas-barrier laminated body to produce the sealed body, and the processing and transportation of the sealed body, the gas The barrier film is disposed on the outermost surface. For this reason, flaws or cracks may occur in the gas barrier film, and the gas barrier properties of the gas barrier film may be reduced. In addition, when the object to be sealed is used as a light-emitting element such as an organic EL element for a display or the like, if a flaw or crack occurs in the gas barrier film, the flaw or crack may become a defect and cause bright spots or the like.

Therefore, the inventors of the present invention, in the process up to the storage and transportation of the gas-barrier laminate, the process of sealing the object to be sealed with the gas-barrier laminate to produce the sealed body, and the processing and transportation of the sealed body, etc. During the process, in order to prevent flaws or cracks in the gas barrier film, it is considered to protect the entire surface of the gas barrier film with a protective film, and to peel off the protective film at the desired timing. The desired timing refers to, for example, the timing when the gas barrier film no longer needs to be protected or the timing when the gas barrier film needs to be exposed. However, after the object to be sealed is sealed with the gas barrier laminate, when the protective film is peeled off, it has been found that a gap may be generated between the object to be sealed and the adhesive layer. When a gap is formed between the object to be sealed and the adhesive layer, oxygen, moisture, etc. may infiltrate through the gap and deteriorate the object to be sealed. In addition, the appearance also becomes poor. On the other hand, in a sealed body sealed by a gas-barrier laminate, even if there is no gap between the object to be sealed and the adhesive layer, oxygen, moisture, etc. may permeate into the object to be sealed due to various reasons, However, the possibility of deterioration of the object to be sealed occurs.

In view of the above problems, the present invention aims to provide a method for producing a gas-barrier laminate and a sealing body using the gas-barrier laminate, in which the gas-barrier laminate is used in the process of storing and transporting the gas-barrier laminate. In the process of sealing the object to be sealed with a gas-barrier laminate to produce the seal, and in the process of processing and transporting the seal, the gas-barrier laminate can prevent flaws or cracks in the gas-barrier film by the protective film, At the same time, when the protective film is peeled off at a desired timing, no gap is generated between the object to be sealed and the adhesive layer, and the durability of the object to be sealed is good. [Means used to solve the problem]

The inventors of the present invention have diligently studied based on the above concept of protecting the gas barrier film with a protective film. As a result, it was found that a gas barrier laminate having a laminated structure in which an adhesive layer, a gas barrier film, and a protective film are sequentially arranged, when the adhesive layer is used as the bonding surface and attached to a glass plate under specific conditions, The above problems can be solved by adjusting the adhesive force between the glass plate and the adhesive layer, and the adhesive force between the gas barrier film and the protective film to satisfy a specific relationship.

That is, the present invention relates to the following [1] to [14]. [1] A gas-barrier laminate comprising: The laminated structure is sequentially arranged with an adhesive layer, a gas barrier film and a protective film, The above-mentioned adhesive layer was used as the bonding surface, and the above-mentioned gas-barrier laminate was pressed against the glass plate under the following condition (α) with a roller. After the above-mentioned gas-barrier laminate was attached to the above-mentioned glass plate, the following condition (β) Peel off, and other conditions follow JIS Z0237:2000 to measure the adhesive force a between the glass plate and the adhesive layer, and the adhesive force b between the gas barrier film and the protective film. The adhesive force a And the above adhesive force b satisfies the following formula (1), a＞b･･･(1) Condition (α): temperature 23°C, pressure 0.2 MPa and speed 0.2 m/min, Condition (β): After attaching, let it stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and then peel it off at a peeling speed of 300 mm/min. [2] The gas barrier laminate according to [1], wherein the adhesive layer is a curable adhesive layer. [3] The gas barrier laminate according to [2], wherein the curable adhesive layer is a layer formed of an adhesive composition containing a polyolefin-based resin (A). [4] The gas barrier laminate according to [3], wherein the polyolefin resin (A) includes a modified polyolefin resin (A1). [5] The gas barrier laminate according to any one of [2] to [4], wherein the curable adhesive layer includes a curable component (B), and the curable component (B) is included in 25 A polyfunctional epoxy resin compound (BL) that is liquid at °C. [6] The gas barrier laminate according to [5], wherein the polyfunctional epoxy resin compound (BL) has a weight average molecular weight (Mw) of 1,500 to 5,000. [7] The gas barrier laminate according to [5] or [6], wherein the content of the polyfunctional epoxy resin compound (BL) is 10 to 34% by mass of the total amount of the adhesive composition. [8] The gas barrier laminate according to any one of [1] to [7], wherein the gas barrier film has a base material layer and a gas barrier layer. [9] The gas barrier laminate according to [8], wherein the base material layer has a resin film, and the resin film contains one or more selected from polycarbonate, cycloolefin polymer, and cycloolefin copolymer as Resin composition. [10] The gas barrier laminate according to [8] or [9], wherein the base material layer has a thickness of 30 μm or less. [11] The gas barrier laminate according to any one of [8] to [10], wherein the gas barrier layer is a polymer layer containing a polymer compound and subjected to a modification treatment. [12] The gas barrier laminate according to any one of [8] to [11], wherein the gas barrier layer and the adhesive layer are directly laminated. [13] The gas barrier laminate according to any one of [1] to [12], wherein the protective film has a protective layer and an adhesive layer, and the adhesive layer is attached to the gas barrier film. [14] A method of manufacturing a sealed body, which sequentially has the following steps (1) to (2), ・Step (1): A step of attaching the gas-barrier laminate described in any one of [1] to [13] to the object to be sealed with the adhesive layer as the bonding surface, ・Step (2): A step of peeling the protective film from the gas barrier laminate. [Invention effect]

According to the present invention, it is possible to provide a gas-barrier laminate and a method for producing a sealed body using the gas-barrier laminate, in which the gas-barrier laminate is used to store and transport the gas-barrier laminate. In the process of sealing the barrier laminate to produce the seal, and in the process of processing and transporting the seal, the gas barrier laminate can prevent flaws or cracks in the gas barrier film through the protective film, and at the desired timing When the protective film is peeled off, no gap occurs between the object to be sealed and the adhesive layer, and the object to be sealed has good durability.

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

[Gas barrier laminate] The gas-barrier laminate of the present invention is a gas-barrier laminate having a laminated structure in which an adhesive layer, a gas-barrier film, and a protective film are disposed in this order. In addition, in the gas barrier laminate of the present invention, the adhesive layer is used as a bonding surface, and the gas barrier laminate is pressed against a glass plate by a roller under the following condition (α). After the board is attached, it is peeled off under the following conditions (β), and other conditions follow JIS Z0237:2000 to measure the adhesion a between the glass plate and the adhesive layer, and the adhesion b between the gas barrier film and the protective film, The above-mentioned adhesive force a and the above-mentioned adhesive force b satisfy the following formula (1): a＞b･･･(1) Condition (α): temperature 23°C, pressure 0.2 MPa and speed 0.2 m/min, Condition (β): After attaching, let it stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and then peel it off at a peeling speed of 300 mm/min. In addition, in this specification, the adhesive force a between a glass plate and an adhesive layer is measured by peeling the gas-barrier laminated body affixed to a glass plate from a glass plate. In addition, the adhesive force b between the gas barrier film and the protective film was measured by peeling the gas barrier layered product attached to the glass plate from the protective film. In addition, in this specification, "gas barrier" refers to the function of preventing gas such as oxygen and water vapor from permeating.

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 protective film are arranged in this order. As the layer configuration of the gas barrier layered product in one aspect of the present invention, for example, the following aspects are listed in which only an adhesive layer, a gas barrier film, and a protective film are laminated in this order, and further examples include: The following aspects of the release sheet of the adhesive layer. ・Adhesive layer/gas barrier film/protective film ・Release sheet/adhesive layer/gas barrier film/protective film The aspect of this layer structure having a release sheet shows the state before using the gas-barrier laminate as a sealing material. When used as a sealing material, the release sheet is peeled and removed, and the surface of the exposed adhesive layer is bonded to the object to be sealed to cover the object to be sealed for sealing. In addition, the removal of the protective film laminated on the gas barrier film is carried out in the process of sealing the object to be sealed with the gas barrier laminate to produce a sealed body, or in the process of processing or transporting the sealed body.

In addition, the layer configuration of the gas-barrier laminate of the present invention becomes, for example, the following aspects after the surface of the exposed adhesive layer is bonded to the object to be sealed and covers the object to be sealed. ・Adhesive layer/gas barrier film/protective film Here, the adhesive agent layer which the gas-barrier laminated body of one aspect of this invention has may be a curable adhesive agent layer. In this case, after curing the curable adhesive layer, the layer configuration of the gas-barrier laminate is as follows. ・Hardened adhesive layer/gas barrier film/protective film In addition, in this invention, a "curable adhesive layer" means an uncured adhesive layer. The gas barrier film is protected by the protective film to prevent flaws or cracks in the gas barrier film from occurring in the sealed body produced by sealing the object to be sealed with the gas barrier laminate of the present invention until the protective film is peeled off. Here, after the protective film is peeled off from the sealing body, the following aspects are obtained. ・Adhesive layer/Gas barrier film Moreover, when the adhesive layer is a curable adhesive layer, the curable adhesive layer is cured and the protective layer is peeled off from the sealing body, and the following aspects are obtained. ・Hardened adhesive layer/gas barrier film In addition, in this specification, what seals the object to be sealed by attaching the surface of the exposed adhesive layer to the object to be sealed and covering the object to be sealed is referred to as a "sealed body". The adhesive layer of the sealing body may be unhardened, hardened, or in an intermediate state between unhardened and hardened, that is, a semi-hardened state. In addition, when the adhesive layer of this sealing body is an uncured or semi-cured state, this sealing body can also be called a "sealing precursor." In addition, in the present invention, the process of hardening the adhesive layer of the sealing body may be included in the process of processing the sealing body.

The inventors of the present invention considered the process of storing and transporting the gas-barrier laminated body, the process of sealing the object to be sealed with the gas-barrier laminated body to produce a sealed body, and the processing and transporting of the sealed body. During the process, in order to prevent flaws and cracks in the gas barrier film, the entire surface of the gas barrier film is protected with a protective film, and the protective film is peeled off at desired timing. However, it has been found that after the object to be sealed is sealed with a gas-barrier laminate, when the protective film is peeled off, a gap will be generated between the object to be sealed and the adhesive layer, and oxygen, water vapor, etc. will infiltrate from the gap and make the object to be sealed Possibility of seal deterioration. Moreover, it was also found that the appearance became poor. In order to investigate the reason, the inventors of this case have made great efforts to study. As a result, it was found that a gap was generated between the object to be sealed and the adhesive layer due to the force applied when the protective film was peeled off. Therefore, in order to solve the above-mentioned problems, the inventors of the present application have made further efforts to study. As a result, it was found that when the gas barrier laminate is attached to the glass plate under specific conditions, by adjusting the adhesive force a between the glass plate and the adhesive layer and the adhesive force b between the gas barrier film and the protective film To satisfy the above formula (1), the above problems can be solved.

Thus, the inventors of the present application found that it is possible to provide a protective film that can be provided even when the protective film is peeled off at any time during the process of sealing the object to be sealed with the gas barrier laminate to produce the sealed body, and the process of processing and transporting the sealed body. There is no gap between the sealant and the adhesive layer, and a gas-barrier laminate that is extremely easy to use in various steps completes the present invention.

[Physical properties of gas barrier laminates] In the gas-barrier laminate of the present invention, the adhesive layer is used as a bonding surface, and the gas-barrier laminate is pressed against a glass plate with a roller under the following condition (α), and the gas-barrier laminate and the glass plate are bonded. Attached, the peeling was carried out under the following condition (β), and other conditions followed JIS Z0237:2000 to measure the adhesion a between the glass plate and the adhesive layer, and the adhesion b between the gas barrier film and the protective film. The force a and the above-mentioned adhesive force b satisfy the following formula (1): a＞b･･･(1) Condition (α): temperature 23°C, pressure 0.2 MPa and speed 0.2 m/min, Condition (β): After attaching, let it stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and 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 protective film, preferably 1.0 N/50mm or more, more preferably It is 2.0N/50mm or more, more preferably 3N/50mm or more, still more preferably 4N/50mm or more, still more preferably 5N/50mm. Moreover, in the gas-barrier laminated body of one aspect of this invention, although the upper limit value of the adhesive force a between a glass plate and an adhesive agent layer is not specifically limited, Usually, it is 20N/50mm.

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

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

Hereinafter, for the adhesive layer, the gas barrier film, and the protective film constituting the laminated structure of the gas barrier laminate of the present invention, the methods for satisfying the adhesive force a between the glass plate and the adhesive layer and the gas barrier film are listed. The specific method of the above formula (1) for the adhesive force b between the protective film and will be described in detail.

[Adhesive layer] The gas barrier laminate of the present invention has an adhesive layer. The adhesive composition constituting the adhesive layer is not particularly limited as long as it satisfies the above formula (1). For example, a dry-curable adhesive composition, a heating-melting adhesive composition, and a curable adhesive composition can be used Compositions and pressure-sensitive adhesive compositions, etc. 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, Adhesive compositions containing rubber, adhesive compositions containing polyolefin resins, adhesive compositions containing epoxy resins, and the like. These adhesive compositions may be used alone or in combination of two or more. In addition, the adhesive composition may contain a binder resin (binder resin) other than the above resins. In addition, the adhesive composition may contain one or more selected from curable components, silane coupling agents, catalysts, polymerization initiators, and tackifiers. Also, the thickness of the adhesive layer is preferably 0.5-300 μm, more preferably 3-200 μm, further preferably 5-150 μm, and still more preferably 5-150 μm, from the viewpoint of ensuring excellent sealing performance of the object to be sealed. 80 μm.

In addition, the water vapor transmission rate of the adhesive layer is preferably 100 g/m ² ･day or less, more preferably 85 g/m ² ･day or less, still more preferably 70g/m ² ･day or less. In addition, in this specification, the "water vapor transmission rate of the adhesive layer" refers to the value measured using a gas transmission rate measuring device (manufactured by Mocon Corporation, product name "PERMATRAN", but other general-purpose water vapor transmission rates may also be used. The measured value of the transmittance measuring device shows the same value.

Here, the adhesive layer included in the gas-barrier laminate according to one aspect of the present invention is preferably a curable adhesive layer. When the adhesive layer is curable, the adhesive layer is in an uncured state at the time of attachment, and can be easily attached to the object to be sealed, and at the same time, it can have good followability to the unevenness of the object to be sealed. Furthermore, by sticking the curable adhesive layer on the object to be sealed and then hardening it, the object to be sealed and the adhesive layer can be strongly bonded. As a result, the gas-barrier laminate is excellent in preventing deterioration of the object to be sealed due to penetration of oxygen, water vapor, and the like. In addition, the water vapor transmission rate of the curable adhesive layer is preferably in the same range as the above-mentioned "water vapor transmission rate of the adhesive layer" from the viewpoint of ensuring good gas barrier properties. The "water vapor transmission rate of the curable adhesive layer" can be measured by the same measuring method as the above-mentioned "water vapor transmission rate of the adhesive layer". The curable adhesive layer can be formed of a curable adhesive composition, specifically, for example, a thermosetting adhesive composition or an energy ray curable adhesive composition that can be cured by heat or energy rays. In addition, the energy ray refers to one having an energy quantum in an electromagnetic wave or a charged particle beam. Examples thereof include ultraviolet rays, electron beams, and the like, and ultraviolet rays are preferred. The curable adhesive layer is preferably a thermosetting adhesive layer formed of a thermosetting adhesive composition.

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

In addition, in one aspect of the present invention, the adhesive composition for forming the curable adhesive layer may contain other components than the polyolefin-based resin (A) and the curable component (B). Examples of the other components include binder resins (A') other than polyolefin resins (A), silane coupling agents (C), curing catalysts (D), and cationic polymerization initiators (D'). , and one or more types of tackifiers (E). In addition, in the description below, "polyolefin resin (A)", "binder resin (A') other than polyolefin resin", "curable component (B)", "silane coupling agent (C)" , "hardening catalyst (D)", "cationic polymerization initiator (D')" and "tackifier (E)" may also be referred to as "component (A)", "component (A')", "Ingredient (B)", "Ingredient (C)", "Ingredient (D)", "Ingredient (D')" and "Ingredient (E)".

In one aspect of the present invention, the total content of the components (A) and (B) in the adhesive composition containing both the polyolefin resin (A) and the curable component (B) is relative to the adhesive composition The total amount (100% by mass) of the active ingredients of the substance is preferably at least 70% by mass, more preferably at least 80% by mass, more preferably at least 90% by mass, further preferably at least 95% by mass, and even more preferably 99% by mass or more, and usually 100% by mass or less. Also, the adhesive composition includes, in addition to the polyolefin resin (A) and the curable component (B), components selected from (A'), (C), (D), (D') and (E ) in the case of one or more types, the components (A) and (B) in the adhesive composition and the components selected from the components (A'), (C), (D), (D') and (E) The total content of one or more components in the adhesive composition is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and even more preferably It is 90-100 mass %, More preferably, it is 95-100 mass %. In addition, in this specification, "the active ingredient of an adhesive agent composition" means the component (solid content) except the diluent solvent contained in an adhesive agent composition.

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

＜Polyolefin resin (A)＞ In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, it is preferable that the adhesive composition contains a polyolefin-based resin (A). In this specification, a "polyolefin resin" means a polymer having a repeating unit derived from an olefin monomer. When the adhesive composition contains the polyolefin resin (A), the water vapor transmission rate of the adhesive layer after curing tends to decrease. Therefore, it is easy to improve the water vapor barrier property of the adhesive layer after hardening. The content of the polyolefin-based resin (A) in the adhesive composition is preferably 30 to 95% by mass, more preferably 40 to 90% by mass relative to the total amount of active ingredients (100% by mass) of the adhesive composition. %, more preferably 50 to 80% by mass. When the content of the polyolefin-based resin (A) is in the above-mentioned range, the water vapor transmission rate of the adhesive layer after hardening will fall more easily. In addition, although the adhesive force a between the glass plate and the curable adhesive layer tends to decrease as the content of the polyolefin-based resin (A) in the adhesive composition increases, when the gas barrier film is added When the adhesive force b with the protective film is adjusted to be lower than the adhesive force a, the above formula (1) can be satisfied. In addition, it is also possible to reduce the content of the polyolefin-based resin (A) in the adhesive composition within the range that satisfies the required water vapor barrier properties, and place a gap between the glass plate and the curable adhesive layer. The adhesive force a is adjusted to a higher value than the adhesive force b to satisfy the above formula (1).

The olefin-based monomer contained in the polyolefin-based resin (A) is preferably an α-olefin having 2 to 8 carbon atoms, among which ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4- Methyl-1-pentene, 1-hexene. Moreover, polyolefin resin (A) may have the unit derived from 2 or more types of α-olefins. In addition, the polyolefin resin (A) may be a polymer composed only of repeating units derived from olefin monomers, or may be a polymer composed of repeat units derived from olefin monomers and A copolymer composed of repeating units of monomers. As a monomer copolymerizable with an olefin type monomer, vinyl acetate, (meth)acrylate, styrene, etc. are mentioned, for example. In addition, in this specification, "(meth)acryl" means both "acryl" and "methacryl", and other similar terms are also the same.

Specific examples of the polyolefin-based resin (A) include ultra-low-density polyethylene (VLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear Low-density polyethylene, polypropylene (PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-( Meth)acrylate copolymers, polyisobutylene, polyisoprene, and the like. These may be used individually or in combination of 2 or more types.

Here, in one aspect of the present invention, when the adhesive layer is a curable adhesive layer, from the viewpoint of further improving the sealability of the adhesive layer after curing, the polyolefin-based resin (A) Preferably, the modified polyolefin resin (A1) is included. In this specification, "modified polyolefin-based resin (A1)" means that the polyolefin-based resin (A) as a precursor reacts with a denaturant, and the functional group of the denaturant is introduced as a side chain into the main chain. Polymer of polyolefin resin (A). In addition, the denaturant may have two or more types of functional groups in the molecule.

As the functional group that the denaturant has, that is, the functional group that can be introduced as a side chain into the polyolefin resin (A) as the main chain, for example, a carboxyl group, a group derived from a carboxylic acid anhydride, a carboxylate group, Hydroxy group, epoxy group, amido group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, phosphono group, phosphone group ), nitro group, urethane group, halogen atom, alkoxysilyl group (alkoxysilyl), etc. Among these functional groups, carboxyl groups, groups derived from carboxylic acid anhydride, carboxylate groups, hydroxyl groups, ammonium groups, amine groups, imide groups, isocyanate groups, and alkoxysilyl groups are preferred, among which is a group derived from carboxylic anhydride.

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

The compound having an acid group is not particularly limited as long as it can be introduced as a side chain into the polyolefin-based resin (A) as the main chain, but unsaturated carboxylic acids and their anhydrides are preferred. Examples of unsaturated carboxylic acids and their anhydrides include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, and tetrahydrophthalein. acid, aconitic acid, maleic anhydride, itaconic anhydride, glutacenediic anhydride, pyrocitric anhydride, ornithic anhydride, norbornedicarboxylic anhydride, tetrahydrophthalic anhydride, and the like. These unsaturated carboxylic acids and their anhydrides may 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.

In addition, acid-modified polyolefin resins may be commercially available. Examples of commercially available acid-modified polyolefin resins include ADMER (registered trademark) (manufactured by Mitsui Chemicals), UNISTOLE (registered trademark) (manufactured by Mitsui Chemicals), Bondy Ram (manufactured by Polyram), orevac ( registered trademark) (manufactured by Arkema Corporation), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.

The amount of the compound that reacts with the polyolefin resin (A) as the precursor and has an acid group is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the polyolefin resin (A) as the precursor, More preferably, it is 0.2-3 mass parts, More preferably, it is 0.2-1.0 mass parts. When the compounding quantity of the compound which has an acid group exists in the said range, it becomes easy to improve the sealing performance of the adhesive agent layer after hardening.

The weight average molecular weight (Mw) of the polyolefin resin (A) and the modified polyolefin resin (A1) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 25,000 to 250,000, still more preferably 30,000~150,000. 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 easily maintain the sheet shape.

In addition, in one aspect of the present invention, the polyolefin-based resin (A) may be composed of modified polyolefin-based resin (A1) only, or may be composed of modified polyolefin-based resin (A1) and non-modified polyolefin Made of resin. The content of the modified polyolefin resin (A1) is preferably 50 to 100 mass %, more preferably 65 to 100 mass % with respect to the total amount (100 mass %) of the polyolefin resin (A), and further preferably Preferably, it is 80-100 mass %, More preferably, it is 90-100 mass %. When the content of the modified polyolefin-based resin (A1) is within the above range, it is easier to improve the sealing performance of the cured adhesive layer.

＜Hardening component (B)＞ In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition contains a curable component (B). In this specification, "curable component (B)" refers to a component that forms a network structure by heating or irradiation of energy rays, and hardens to an insoluble and insoluble state. When the adhesive composition contains the curable component (B), the adhesive layer becomes curable, and the sealing performance of the cured adhesive layer is improved. In addition, the curable component (B) may be a thermosetting component or an energy ray curable component, preferably a thermosetting component. The content of the hardening 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 of active ingredients (100% by mass) of the adhesive composition , more preferably 5 to 45% by mass, further preferably 10 to 40% by mass. When the content of the curable component (B) is within the above range, it is easier to improve the sealing performance of the cured adhesive layer. In addition, when the adhesive composition includes polyolefin resin (A), the content of curable component (B) is preferably 5 parts by mass relative to 100 parts by mass of polyolefin resin (A) in the adhesive composition. ~110 parts by mass, more preferably 10~100 parts by mass. When the adhesive layer formed from the adhesive composition having the curable component (B) content in this range is cured, the water vapor barrier property of the cured adhesive layer is further excellent.

Examples of the curable component (B) include curable epoxy resins, melamine resins, urea resins, and maleimide resins. These can be used individually or in combination of 2 or more types. Among these, it is preferable to include a curable epoxy resin (B1). In this specification, "curable epoxy resin (B1)" refers to an epoxy compound that forms a network structure by heating or irradiation of energy rays, and hardens to an insoluble and infusible state.

Moreover, it is preferable that curable epoxy resin (B1) contains polyfunctional epoxy resin (B2). In this specification, "polyfunctional epoxy resin (B2)" means the compound which has at least 2 or more epoxy groups in a molecule|numerator.

From the viewpoint of further improving the sealing performance of the adhesive layer after curing, the multifunctional epoxy resin (B2) is preferably a bifunctional epoxy resin having two epoxy groups in the molecule. Bifunctional epoxy resins include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether. Ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac type epoxy resin (for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cresol novolak type epoxy resin Aromatic epoxy compounds such as epoxy resins, brominated phenol novolac epoxy resins); alicyclic compounds such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, etc. Epoxy compound; pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl hexahydrophthalate, neopentyl glycol Diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,2-bis(3-glycidyl-4-glycidyloxyphenyl)propane, dimethylolpropane polyglycidyl ether, dimethylolpropane polyglycidyl ether, dimethylolpropane polyglycidyl ether Aliphatic epoxy compounds such as alkane diglycidyl ether (dimethylol tricyclodecane diglycidyl ether) and the like. These bifunctional epoxy resins may be used alone or in combination of two or more.

Here, in one aspect of the present invention, the adhesive composition preferably contains a multifunctional epoxy resin compound (BL) which is liquid at 25° C. as the component (B). In the description below, the polyfunctional epoxy resin compound (BL) which is liquid at 25° C. is also referred to as “component (BL)”. When the adhesive composition is exposed to high temperature, the component (BL) has the effect of reducing the storage modulus of the adhesive composition (hereinafter also referred to as "storage modulus reduction effect"). Therefore, in one aspect of the present invention, when the adhesive composition contains this component (BL), it is possible to efficiently form an adhesive layer excellent in conformability to unevenness.

The weight average molecular weight (Mw) of the component (BL) is preferably 1,000 or more, more preferably 1,200 or more, and still more preferably 1,500 from the viewpoint of suppressing the outgassing (outgas) caused by the component (BL). Above, more preferably above 1,800, still more preferably above 2,100. Moreover, the weight average molecular weight (Mw) of the component (BL) is preferably 5,000 or less, more preferably 4,500 or less from the viewpoint of being an adhesive composition that further enhances the effect of reducing the storage modulus. The adhesive force a between the glass plate and the curable adhesive layer changes depending on the magnitude of the weight average molecular weight (Mw) of the component (BL). Specifically, the larger the weight average molecular weight (Mw) of the component (BL) in the adhesive composition, the greater the adhesive force a tends to decrease. However, when the adhesive force b between the gas barrier film and the protective film is adjusted to a ratio of When the value of the force a is lower, the above formula (1) can be satisfied. In addition, within the range that satisfies the required outgassing suppression performance, the weight average molecular weight (Mw) of the component (BL) is lowered, and the adhesive force a between the glass plate and the curable adhesive layer is adjusted to a ratio of Higher values of the force b can also satisfy the above formula (1).

The epoxy equivalent of the component (BL) is preferably 100 to 1,500 g/eq, more preferably 150 to 1,500 g/eq, further preferably 200 to 1,400 g/eq, still more preferably 240 to 1,300 g/eq. In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and is a value measured in accordance with JIS K7236:2009.

The content of the component (BL) in the adhesive composition is preferably 5 to 40% by mass, more preferably 8 to 36% by mass relative to the total amount of active ingredients (100% by mass) of the adhesive composition, and further Preferably it is 10-34 mass %. When the content of the component (BL) is within this range, the effect of lowering the storage modulus can be obtained, and the occurrence of outgassing due to the component (BL) can also be suppressed. The adhesive force a between the glass plate and the curable adhesive layer changes with the increase or decrease of the content of the component (BL). When there is little content of the component (BL) in an adhesive composition, there exists a tendency for adhesive force a to fall. At this time, when the adhesive force b between the gas barrier film and the protective film is adjusted to a lower value than the adhesive force a, the above formula (1) can be satisfied. Also, increasing the content of the component (BL) in the adhesive composition and adjusting the adhesive force a between the glass plate and the curable adhesive layer to a value higher than the adhesive force b can satisfy the above formula ( 1).

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

＜Silane coupling agent (C)＞ In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a silane coupling agent (C). In this specification, "silane coupling agent (C)" refers to 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 cured adhesive layer even in any environment of normal temperature or high temperature environment. In addition, even when the adhesive layer is not curable, the adhesive composition may contain a silane coupling agent (C). Also in this case, it is easy to ensure the sealing performance of the adhesive layer well. The content of the silane coupling agent in the adhesive composition is preferably 0.01-0.1 mass %, more preferably 0.02-0.09 mass %, based on the total amount (100 mass %) of the adhesive composition. In addition, when the adhesive composition includes a polyolefin resin (A), the content of the silane coupling agent (C) in the adhesive composition is preferably 100 parts by mass of the polyolefin resin (A). 0.01 to 5.0 parts by mass, more preferably 0.05 to 1.0 parts by mass. When the content of the silane coupling agent (C) is within the above range, even if exposed to high temperature and high humidity environment for a long time, it is easy to ensure good sealing performance of the cured adhesive layer.

As the silane coupling agent (C), it is preferable that at least one of the silane coupling agents in the molecule has at least one An alkoxysilyl-based organosilicon compound. Examples of the silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimetroxysilane), 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Silicon compounds with epoxy structure such as 8-glycidoxyoctyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Amino-containing silicon compounds such as trimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3- Isocyanate propyltriethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.

＜Hardening catalyst (D)＞ In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably contains a curing catalyst (D). In this specification, a "curing catalyst (D)" means a catalyst that promotes the reaction of curing the curable component (B) by heat or energy rays. When the adhesive composition contains the curing catalyst (D), it is easy to improve the sealing performance of the cured adhesive layer at high temperature. The content of the curing catalyst (D) contained in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the curable component (B). When the content of the curing catalyst (D) is in the above range, it is easier to improve the sealing performance of the cured adhesive layer at high temperature.

When the curable component (B) is a thermosetting component, the curing catalyst (D) is preferably a thermosetting curing catalyst, that is, an imidazole-based hardening catalyst. Examples of imidazole-based curing catalysts include 2-methylimidazole, 2-benzimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like. These imidazole type hardening catalysts can be used individually or in combination of 2 or more types. Among these imidazole-based curing catalysts, 2-ethyl-4-methylimidazole is preferred.

＜Cationic polymerization initiator (D')＞ In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition preferably further contains a cationic polymerization initiator (D'). When the adhesive layer is a thermosetting adhesive layer, the cationic polymerization initiator (D') is preferably a photocationic polymerization initiator. Examples of thermal cationic polymerization initiators include perium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like, and percite salts are preferred. Examples of photocationic polymerization initiators include cobalt-based compounds, iodonium-based compounds, phosphonium-based compounds, ammonium-based compounds, antimonate-based compounds, diazonium-based compounds, and selenium-based compounds. , oxonium salt-based compounds, bromide-based salt-based compounds, etc., preferably oxonium-based salt-based compounds. 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 aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition may contain a tackifier (E). The tackifier (E) used in one aspect of the present invention is a component that assists in improving the adhesive properties of the curable adhesive layer, and generally refers to an oligomer with a weight average molecular weight (Mw) of less than 10,000, and What can be distinguished from the resin (X) contained in the adhesive composition mentioned later. In addition, when the adhesive layer is not curable, the adhesive composition may contain a tackifier (E). The weight average molecular weight (Mw) of a tackifier (E) is usually less than 10,000, but is preferably 400-8000, more preferably 500-5000, and more preferably 800-3500.

From the viewpoint of suppressing the outgassing caused by the tackifier (E), the content of the tackifier (E) in the adhesive composition is preferably reduced, relative to the total active ingredients of the adhesive composition The amount (100 mass %) is preferably greater than 0 mass % and 30 mass % or less, more preferably greater than 0 mass % and 15 mass % or less, further preferably 1 to 10 mass %. Also, when it is desired to suppress the occurrence of outgassing as much as possible, the adhesive composition may preferably not contain a tackifier (E). In addition, the content of the tackifier (E) contained in the adhesive composition is preferably greater than 0 parts by mass to 80 parts by mass, more preferably greater than 0 parts by mass, relative to 100 parts by mass of the polyolefin resin (A). ~30 parts by mass, more preferably 1~20 parts by mass. Also, when it is desired to suppress the occurrence of outgassing as much as possible, the content of the tackifier (E) is preferably as small as possible, more preferably 0 part by mass, based on 100 parts by mass of the polyolefin resin (A). On the other hand, when the content of the tackifier (E) in the adhesive composition is small, the adhesive force a between the glass plate and the curable adhesive layer tends to decrease. In this case, by adjusting the adhesive force b between the gas barrier film and the protective film to a lower value, the above formula (1) can be satisfied. In addition, by increasing the content of the tackifier (E) in the adhesive composition within the range that satisfies the required outgassing suppression performance, the adhesive force between the glass plate and the curable adhesive layer can be improved. If a is adjusted to a higher value than the adhesive force b, the above formula (1) can also be satisfied.

Examples of the tackifier (E) include rosin-based resins such as polymerized rosin, polymerized rosin ester, and rosin derivatives; polyterpene resins (polyterpene resins), aromatic modified terpene resins, and hydrogenated products thereof, Terpene resins such as terpene phenol resins; coumarone-indene resins; aliphatic petroleum resins, aromatic petroleum resins and their hydrogenated products, aliphatic/aromatic copolymer petroleum resins, etc. Petroleum resins; styrene or styrene-substituted polymers; α-methylstyrene (α-methylstyrene) single-polymer resins, copolymers of α-methylstyrene and styrene, styrene-based monomers and Copolymers of aliphatic monomers, copolymers of styrene monomers and α-methylstyrene and aliphatic monomers, homogeneous polymers composed of styrene monomers, styrene monomers and aromatic Styrenic resins such as copolymers of family monomers, etc. These tackifiers (E) may be used alone or in combination of two or more. Among them, the tackifier (E) is preferably a styrene-based resin, more preferably a copolymer of a styrene-based monomer and an aliphatic monomer.

The softening point of the tackifier (E) is preferably Above 80°C, more preferably 85~170°C, further preferably 90~150°C. In addition, in this specification, a softening point means the value measured based on JISK5902. When using 2 or more types of tackifiers (E), it is preferable that the weighted average of the softening point of these tackifiers falls within the said range.

>Other additives> In one aspect of the present invention, the adhesive composition may contain other additives other than the above-mentioned components (A) to (E) within a range that does not greatly impair the effect of the present invention. Other additives can be appropriately selected depending on the application, and examples thereof include additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, and softeners. These additives may be used alone or in combination of two or more. In addition, when the adhesive layer is not curable, the adhesive composition may contain these additives.

>Dilution medium> In one aspect of the present invention, from the viewpoint of improving the formability of the adhesive layer, the adhesive composition may further contain a diluting solvent. The diluting solvent can be appropriately selected from organic solvents, but specifically, aromatic hydrocarbon-based solvents such as benzene and toluene; ester-based solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl acetate, and the like; Ketone-based solvents such as ketone and methyl isobutyl ketone; aliphatic hydrocarbon-based solvents such as n-pentane, n-hexane, and n-heptane; alicyclic solvents such as cyclopentane, cyclohexane, and methylcyclohexane Hydrocarbon solvents, etc. These solvents may be used alone or in combination of two or more. In addition, the content of the solvent can be appropriately set in consideration of applicability and the like. Also, even when the adhesive layer is not curable, the adhesive composition may contain a diluting solvent from the same viewpoint.

>Formation method of adhesive layer> The method for forming the adhesive layer constituting the gas-barrier laminate of the present invention is not particularly limited, and it can be formed appropriately using a known method or the like. Here, in one aspect of the present invention, the adhesive layer is preferably formed of the above-mentioned adhesive composition. For example, there may be mentioned a method 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, heat treatment with heat at the time of drying the coating film does not include the curable adhesive layer. layer hardening.

Examples of coating methods for the adhesive composition include spin coating, spray coating, bar coating, blade coating, roll coating, blade coating, and die coating. method, gravure coating method, etc. Also, from the viewpoint of improving applicability, it is preferable to add the above-mentioned dilution solvent to the adhesive composition to form a solution. As the drying conditions when drying the coating film, for example, it is preferable to apply a drying treatment at 80 to 130° C., preferably 90 to 110° C., for 30 seconds to 5 minutes.

[Gas barrier film] The gas barrier laminate of the present invention has a gas barrier film. The gas barrier film is laminated on the adhesive layer. Since the gas-barrier laminate of the present invention has a gas-barrier film, it can exhibit excellent gas-barrier properties with a high effect of preventing the permeation of gases such as oxygen and water vapor. Also, in the gas barrier laminate of the present invention, a protective film is laminated on the gas barrier film so that the gas barrier film is protected by the protective film. Therefore, in addition to the storage or transportation up to the use of the gas-barrier laminated body, in the process of sealing the object to be sealed with the gas-barrier laminated body to produce a sealed body, and in the process of processing and transporting the sealed body, etc., It is possible to prevent flaws or cracks from occurring in the gas barrier film.

In one aspect of the present invention, the gas barrier film included in the gas barrier laminate has at least a base material layer, and is preferably a film having a gas barrier function. One aspect of the gas barrier film includes a film having a base material layer and a gas barrier layer. For example, the aspect which has the following layer structure is mentioned. ・Substrate layer/Gas barrier layer In addition, in the aspect of the above-mentioned "substrate layer/gas barrier layer", in order to improve the adhesion between the substrate layer and the gas barrier layer, a Adhesion-promoting coating (anchor coat layer). ・Substrate layer／Adhesion-promoting coating／Gas barrier layer

In one aspect of the present invention, the base material layer itself of the gas barrier film of the gas barrier laminate has a gas barrier function, and the base layer may be a single-layer resin having a function as a gas barrier layer. film etc.

In one aspect of the present invention, the gas barrier laminate is, for example, preferably in the following aspect, wherein the gas barrier layer is disposed closer to the adhesive layer than the base material layer. ・Substrate layer/Gas barrier layer/Adhesive layer Thereby, since the base material layer is not interposed between the gas barrier layer and the adhesive layer, the water vapor blocking performance of the gas barrier layered product is further improved. Furthermore, in the case of a configuration in which the gas barrier layer is disposed closer to the adhesive layer than the base material layer, the protective film is laminated on the base material layer of the gas barrier film. Since the base material layer uses the resin film mentioned later, it becomes easy to improve the adhesiveness of a protective film and a base material layer. Also, even when the protective film is not directly laminated on the base layer, but is laminated via some organic substances provided on the base layer, the adhesion between the protective film and the base layer can be easily improved. However, since the gas barrier laminate of the present invention is adjusted to satisfy the relationship of the above formula (1), no gap is generated between the object to be sealed and the adhesive layer when the protective film is peeled off.

In one aspect of the present invention, the water vapor transmission rate of the gas barrier film included in the gas barrier laminate is preferably 0.1 g/m ² / day or less, more preferably 0.05 g/m ² /day or less, further preferably 0.005 g/m ² /day or less. By making the water vapor permeability of the gas barrier film 0.1 g/m ² /day or less, it is easy to effectively suppress the deterioration of the object to be sealed using the gas barrier laminate. For example, penetration of oxygen, water vapor, etc. into elements such as an organic EL element formed on a transparent substrate is suppressed, and deterioration of electrodes and organic layers is easily and effectively suppressed. Also, for a gas barrier laminate having a gas barrier film and an adhesive layer, the water vapor transmission rate is preferably the same value as above in an environment with a temperature of 40° C. and 90% RH (relative humidity). In addition, in this specification, the "water vapor transmission rate of the gas barrier film" refers to the value measured using a gas transmission rate measuring device (manufactured by Mocon Corporation, product name "AQUATRAN 2"), but it may also mean that other general-purpose The same value as the measured value of the water vapor transmission rate measuring device.

In one aspect 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 JIS K7136:2000 is preferably at least 80%, more preferably at least 85%, even more preferably at least 90%. Also, the b ^* value in the L ^* a ^* b ^* display color system measured in accordance with JIS K7136:2000 is preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less.

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

＜Substrate layer＞ As the base layer of the gas barrier film, a resin film containing a resin component is preferable. Examples of the resin component include polyimide, polyamide, polyamide-imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyene, poly Ester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, cycloolefin copolymer, aromatic polymer, and polyurethane polymers. Among these, polycarbonate, cycloolefin-based polymers, and cycloolefin-based copolymers are preferred from the viewpoint of being highly transparent and optically isotropic gas barrier films. In addition, these resins can be used individually or in combination of 2 or more types. Moreover, the base material layer may laminate|stack two or more types of resin films. A resin film with optical isotropy is a better resin film as a constituent material of a gas barrier film when a light-emitting element such as an organic EL element is used for display purposes, but it is difficult to handle due to poor flexibility and fragility. The disadvantage of being prone to blemishes or cracks. In the gas-barrier laminate of the present invention, even when a poorly flexible and brittle resin film such as polycarbonate, cycloolefin-based polymer, and cycloolefin-based copolymer is used as a constituent material of the gas-barrier film, Since the gas barrier film is protected by the protective film, it is possible to prevent flaws or cracks from occurring in the gas barrier film during handling, and it is possible to suppress defects such as bright spots caused by the flaws or cracks from occurring in the display. Therefore, yield can be improved in a display manufacturing process using a light-emitting element such as an organic EL element or the like.

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

＜Gas barrier layer＞ From the viewpoint of being able to reduce the thickness of the gas barrier film and have excellent gas barrier properties, the gas barrier layer of the gas barrier film preferably contains an inorganic film and a polymer compound, and is subjected to a modification treatment. The polymer layer, more preferably the polymer layer. Since the polymer layer is a gas barrier layer, the gas barrier layer can be made flexible and has excellent durability against bending of the gas barrier film.

Examples of the polymer compound contained in the polymer layer include silicon-containing polymer compounds such as polyorganosiloxane (polyorganosiloxane) and polysilazane-based compounds, polyimide, polyamide, polyamide Amide, polyphenylene ether, polyether ketone, polyether ether ketone, polyene, polyester, polycarbonate, polyether, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer substances, aromatic polymers, etc. These polymer compounds may be used alone or in combination of two or more. Among them, the polymer compound contained in the polymer layer is preferably a silicon-containing polymer compound, more preferably a polysilazane-based compound, from the viewpoint of being able to form a gas barrier layer having excellent gas barrier properties. The number average molecular weight of the polysilazane compound is preferably from 100 to 50,000.

Polysilazane compounds are polymers with repeating units containing -Si-N-bonds (silazane bonds) in the molecule. Specifically, it is preferred to have the following general formula (I): Polymers of repeating units.[Chemical 1]

In the above general formula (I), n represents the number of repeating units and represents an integer of 1 or more. Rx, Ry, and Rz independently represent a hydrogen atom, unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted Aryl or alkylsilyl. Among them, 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. In addition, the polymer compound contained in the gas barrier layer may be an inorganic polysilazane in which all of Rx, Ry, and Rz in the general formula (I) are hydrogen atoms, or may be at least one of Rx, Ry, and Rz. An organopolysilazane with a group other than a hydrogen atom.

A polysilazane type compound can be used individually or in combination of 2 or more types. In addition, as the polysilazane-based compound, a modified polysilazane can also be used, or a commercially available product can also be used.

The above-mentioned polymer layer may contain other components in addition to the above-mentioned polymer compound within the range that does not impair the effect of the present invention. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, and flame retardants. These may be used alone or in combination of two or more. The content of the polymer compound in the polymer layer is preferably 50% with respect to the total amount of components in the polymer layer (100% by mass) from the viewpoint of forming a gas barrier layer having more excellent gas barrier properties. ~100% by mass, more preferably 70~100% by mass, further preferably 80~100% by mass.

Also, the thickness of the polymer layer included in the gas barrier film is preferably 50 to 500 nm, more preferably 50 to 300 nm, further 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 in the nano order.

As a method for forming a polymer layer, for example, an easy-to-use spray coater, knife coater, gravure coater, etc. A method in which a coating film is formed by coating with a known device such as a cloth machine, 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 may be performed alone or in combination of two or more. The ion implantation treatment is a method of implanting ions into the polymer layer to modify the polymer layer as described later. Plasma treatment is a method in which the polymer layer is exposed 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 ultraviolet rays to the polymer layer. For example, the ultraviolet modification treatment can be performed according to the method described in JP-A-2013-226757. Among them, from the viewpoint of being able to efficiently modify the inside of the polymer layer without roughening the surface of the polymer layer, and form a gas barrier layer with better gas barrier properties, the modification treatment of the polymer layer is preferably for ion implantation.

In the ion implantation process, the ions to be implanted into the polymer layer include, for example, ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorine carbon (fluorocarbon), hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, Ions of fluorine, sulfur, etc.; ions of alkane-based gases such as methane and ethane; ions of olefin-based gases such as ethylene and propylene; ions of alkadiene-based gases such as pentadiene and butadiene Ions; ions of alkyne-based gases such as acetylene; ions of aromatic hydrocarbon-based gases such as benzene and toluene; ions of cycloalkane-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene Ions; metal ions; ions of organosilicon compounds, etc. These ions may be used alone or in combination of two or more. Among them, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred, and more preferred are Argon ions.

The method for implanting ions is not particularly limited. For example, a method of irradiating ions (ion beams) accelerated by an electric field, a method of injecting ions in plasma (ions of plasma-generated gas), etc., are preferred. The method of injecting ions in plasma is preferable because it can be easily to obtain a gas barrier layer. The ion implantation method in plasma, for example, can generate plasma under the atmosphere including plasma generating gas, and apply a negative high-voltage pulse to the ion-implanted layer, so that the ions (cations) in the plasma can be injected into the ion-implanted layer The surface part is injected.

Examples of the inorganic film used as the gas barrier layer include films formed by vapor phase deposition of inorganic compounds or metals. Examples of raw materials for the inorganic compound film 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; inorganic sulfides; inorganic nitrogen oxides such as silicon oxynitride; inorganic carbon oxides; inorganic nitrogen carbides; inorganic nitrogen oxide carbides, etc. Examples of the raw material of the metal film include aluminum, magnesium, zinc, and tin. These may be used alone or in combination of two or more. Among them, from the viewpoint of gas barrier properties, inorganic films using inorganic oxides, inorganic nitrides, or metals as raw materials are preferred, and furthermore, from the viewpoint of transparency, inorganic oxides or inorganic nitrides are preferred. Inorganic membranes as raw materials. In addition, the inorganic film may be a single layer or a multilayer.

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

Examples of vapor-phase film-forming methods for forming inorganic films include PVD (Physical Vapor Deposition) methods such as vacuum evaporation, sputtering, and ion plating, thermal CVD, plasma CVD, and optical CVD. CVD method (chemical vapor deposition method) etc.

＜Adhesion-promoting coating＞ In one aspect of the present invention, from the viewpoint of further improving the adhesion between the base material layer and the gas barrier layer, an adhesion-promoting coating layer may be provided between the base material layer and the gas barrier layer. As an anchor coating layer, for example, a layer obtained by curing a composition containing an ultraviolet curable compound can be mentioned. The composition containing the ultraviolet curable compound may contain inorganic fillers such as silicon oxide particles. The thickness of the adhesion-promoting coating is preferably 0.1-10 μm, more preferably 0.5-5 μm.

[Protective film] The gas barrier laminate of the present invention has a protective film. The protective film is laminated on the gas barrier film to protect the gas barrier film. In addition, even if the protective film is peeled off at desired timings such as when the gas barrier film does not need to be protected or when the gas barrier film needs to be exposed, no gap will be generated between the object to be sealed and the adhesive layer, and oxygen will be prevented. , water infiltration. In addition, appearance defects can also be prevented.

In one aspect of the present invention, the protective film of the gas barrier laminate has at least a protective layer. As an aspect of the protective film, a single protective layer may be used, but a laminated structure of a protective layer and an adhesive layer is preferable. By adjusting the adhesive force of the protective film through the lamination structure of the protective layer and the adhesive layer, it is easy to obtain a gas-barrier laminate satisfying the above formula (1).

Furthermore, since the gas barrier laminate of the present invention has a protective film, it is possible to reduce the thickness of the base material layer of the gas barrier film and improve the handling properties of the gas barrier laminate. In one aspect of the present invention, the total thickness of the base material layer of the protective film and the gas barrier film is preferably 40-500 μm, more preferably 40-200 μm, further preferably 50-150 μm.

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

＜Protective layer＞ As a protective layer which a protective film has, it is preferable that it is a resin film containing a resin component. As the resin component, among the resin components exemplified as the base material layer of the gas barrier film, those with high impact resistance are preferable. Examples of such resin components include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyene, polyester, polyamide, polyethersulfide , polyphenylene sulfide, polyarylate, acrylic resins, aromatic polymers, and polyurethane polymers. In addition, these resins can be used individually or in combination of 2 or more types. Moreover, the film which colored these can also be used. By applying coloring, it is possible to easily determine the presence or absence of the protective film, and it is convenient to peel off the protective film because the interface between the gas barrier film and the protective film can be easily recognized.

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

The ratio of the thickness of the protective layer of the protective film to the thickness of the substrate layer of the gas barrier film (thickness of the protective layer/thickness of the substrate layer) can automatically reduce the thickness of the substrate layer and improve the handling of the gas barrier laminate. From the viewpoint of sex, it is preferably 1-5, more preferably 1.2-4.5, further preferably 1.5-4.

＜Adhesive layer＞ The adhesive layer which the protective film has is laminated|stacked on one surface of a protective layer, and is a layer for bonding a protective layer and a gas barrier film. Here, from the viewpoint that the gas-barrier laminate of the present invention satisfies the relationship of the above formula (1), it is preferable to lower the adhesive force b between the gas-barrier film and the protective film. By reducing the adhesiveness of the adhesive layer of the protective film, the adhesive force b between the gas barrier film and the protective film can be lowered. As a method of reducing the adhesiveness of the adhesive layer which a protective film has, for example, thinning the thickness of an adhesive layer, changing the kind of adhesive layer, etc. are mentioned. In addition, the adhesive layer included in the gas-barrier laminate of the present invention must impart properties required for sealing the object to be sealed. Therefore, instead of changing the adhesive force a by adjusting the types of raw materials or the amount of raw materials used to form the adhesive composition for forming the adhesive layer, by adjusting only the adhesive that controls the adhesion characteristics to the gas barrier film It is easier to change the adhesive force b by changing the adhesiveness of the layer.

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

The type of the adhesive layer can be changed according to the selection of the resin of the polymer contained in the adhesive composition for forming the adhesive layer. Hereinafter, the selection of the polymer-based resin for the adhesive composition for forming the adhesive layer will be described.

＜Adhesive composition＞ The adhesive composition of the formation material of an adhesive layer contains resin (X) of a polymer. Resin (X) itself may or may not have adhesiveness. In the case where the resin (X) does not have adhesiveness, the adhesive layer formed from the adhesive composition can be made to exhibit adhesiveness by adding a tackifier described later to the adhesive composition. Moreover, in one aspect of this invention, components other than resin (X) contained in an adhesive composition can be adjusted suitably as needed. For example, in one aspect of the present invention, the adhesive composition may further contain one selected from the group consisting of a tackifier and a crosslinking agent from the viewpoint of adjusting the adhesive force within a desired range. In addition to the above, one or more kinds selected from the group consisting of additives for adhesives used for diluting solvents and general adhesives may be contained.

(resin (X)) The weight average molecular weight (Mw) of the resin (X) is preferably at least 10,000, more preferably 10,000 to 2 million, further preferably 20,000 to 1,500,000. Examples of the resin (X) contained in the adhesive composition include acrylic resins, urethane resins, olefin resins, urethane acrylate resins, and polyester resins. These resins (X) may be used alone or in combination of two or more. Also, when these resins (X) are copolymers having two or more constituent units, the form of the copolymer is not particularly limited, and may be block copolymers, random copolymers, or graft copolymers. ) in either. Here, the resin (X) is preferably an acrylic resin from the viewpoint of properly adjusting the adhesiveness of the adhesive layer formed of the adhesive composition and reducing the adhesive force b between the gas barrier film and the protective film. Resin, olefin resin, more preferably acrylic resin.

The content of the resin (X) in the adhesive composition is preferably 30 to 99.99 mass %, more preferably 40 to 99.95 mass %, and more preferably Preferably, it is 50-99.90 mass %, More preferably, it is 55-99.80 mass %, More preferably, it is 60-99.50 mass %. Hereinafter, in one aspect of the present invention, an acrylic resin and an olefin resin that are preferable as the resin (X) will be described.

(acrylic resin) In one aspect of the present invention, from the viewpoint of appropriately adjusting the adhesiveness of the adhesive layer formed of the adhesive composition to lower the adhesive force b between the gas barrier film and the protective film, the adhesive composition The resin (X) to be contained preferably contains an acrylic resin. The content ratio of the acrylic resin in the resin (X) is preferably 30 to 100% by mass, more preferably 50 to 100% in the total amount (100% by mass) of the resin (X) contained in the adhesive composition. % by mass is more preferably 70 to 100% by mass, further more preferably 85 to 100% by mass.

As the acrylic resin that can be used as the resin (X), for example, a polymer containing a structural unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, a polymer containing a structural unit derived from an alkyl (meth)acrylate having a cyclic A polymer of structural units of (meth)acrylate, etc.

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

The acrylic resin is preferably an acrylic polymer (A0) having a constituent unit (a1) derived from an alkyl (meth)acrylate (a1') (hereinafter also referred to as "monomer (a1')") , more preferably an acrylic copolymer (A1) having a structural unit (a1) and a structural unit (a2) derived from a functional group-containing monomer (a2') (hereinafter also referred to as "monomer (a2')") .

The carbon number of the alkyl group that the monomer (a1') has is preferably 1-24, more preferably 1-12, from the viewpoint of easy reduction of the adhesive force accompanying the thinning of the adhesive layer. In addition, the alkyl group of the monomer (a1') may be a straight-chain alkyl group or a branched-chain alkyl group.

Examples of the monomer (a1') include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid 2-Ethylhexyl, lauryl (meth)acrylate, tridecyl (meth)acrylate, octadecyl (meth)acrylate, etc. The monomer (a1') is preferably methyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, more preferably butyl (meth)acrylate , and 2-ethylhexyl (meth)acrylate. These monomers (a1') may be used alone or in combination of two or more. Among them, the monomer (a1') is preferably used in combination of butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Also, the mass ratio [butyl (meth)acrylate/2-ethylhexyl (meth)acrylate] is preferable from the viewpoint of easily reducing the adhesive force b between the gas barrier film and the protective film. It is 1/9 to 5/5, more preferably 1/9 to 4/6, further preferably 1/9 to 3/7.

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

The functional group possessed by the monomer (a2') reacts with a cross-linking agent that may be contained in the adhesive composition described later, and refers to a functional group that can serve as a cross-linking origin or a functional group that has a cross-linking accelerating effect, and examples thereof include , hydroxyl, carboxyl, amino, epoxy, etc. That is, examples of the monomer (a2') include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, and the like. These monomers (a2') may be used alone or in combination of two or more. The monomer (a2') is preferably a hydroxyl-containing monomer or a carboxyl-containing monomer.

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

As the carboxyl group-containing monomer, for example, ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, pyro Ethylenically unsaturated dicarboxylic acids such as citric acid and their anhydrous substances; 2-carboxyethyl (meth) acrylate), etc. The monomer (a2') is preferably 2-hydroxyethyl (meth)acrylate. These monomers (a2') may be used alone or in combination of two or more.

The content of the structural unit (a2) is preferably 0.1 to 40 mass %, more preferably 0.3 to 30 mass %, further preferably 0.5 mass % in the total structural units (100 mass %) of the acrylic copolymer (A1). ~20% by mass, more preferably 0.7~10% by mass. There exists a tendency for the adhesive force b between a gas barrier film and a protective film to become low, so that content of the structural unit (a2) which is a crosslinking origin increases.

The acrylic copolymer (A1) may further contain 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% by mass in the total structural units (100% by mass) of the acrylic copolymer (A1). %, more preferably 80-100 mass%, further preferably 85-100 mass%, further preferably 90-100 mass%.

Examples of the monomer (a3') include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; butadiene, isoprene, and chloroprene. Diene monomers; (meth) cyclohexyl (meth) acrylate, (meth) benzyl (meth) acrylate, (meth) isobornyl acrylate (isobornyl (meth) acrylate), (meth) dicyclopentanyl (meth) acrylate, (meth) dicyclopentenyl (meth) acrylate, (meth) dicyclopentanyl (meth) acrylate Dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate and other (meth)acrylates with a ring structure; styrene, α-methylbenzene Ethylene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloyl morpholin (( meth)acryloylmorpholine), N-vinylpyrrolidone (vinylpyrrolidone) and the like. These monomers (a3') may be used alone or in combination of two or more. As the monomer (a3'), vinyl acetate is preferred.

(Olefin resin) The olefin-based resin that can be used as the resin (X) is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene. These olefin resins may be used alone or in combination of two or more. Specific olefin-based 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 Copolymers of other α-olefins, copolymers of propylene and other α-olefins, copolymers of ethylene and propylene and other α-olefins, copolymers of ethylene and other ethylenically unsaturated monomers (ethylene-vinyl acetate copolymers , ethylene-(meth)acrylate copolymer, ethylene-vinyl alcohol copolymer, etc.), etc. Among them, it may also be a copolymer of ethylene and other ethylenically unsaturated monomers, preferably an ethylene-vinyl acetate copolymer. In addition, examples of the aforementioned α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4 -Methyl-1-hexene, etc. As said ethylenically unsaturated monomer, vinyl acetate, an alkyl (meth)acrylate, vinyl alcohol, etc. are mentioned, for example.

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

Examples of PIB-based resins include polyisobutylene, a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and the These copolymers are brominated or chlorinated, such as halogenated butyl rubber, etc. Among them, a copolymer of isobutylene and isoprene is preferable.

In addition, when the PIB-based resin is a copolymer, the maximum amount of structural units composed of isobutylene can be contained in the total structural units. The content of the structural unit composed of isobutylene is preferably 80 to 100 mol %, more preferably 90 to 100 mol %, and still more preferably 95~100 mole%. These PIB-type resins can be used individually or in combination of 2 or more types.

Moreover, when using a PIB-type resin, it is preferable to use together the crosslinkable rubber-type resin, such as polyisoprene rubber which has a carboxylic acid type functional group.

(crosslinking agent) In one aspect of the present invention, the adhesive composition contains an acrylic copolymer having structural units (a1) and (a2), and a resin (X) having the aforementioned functional groups such as a rubber-based resin capable of cross-linking reaction. , preferably further contains a crosslinking agent. This crosslinking agent reacts with the functional group which this resin (X) has, and crosslinks resins. The adhesive force b between the gas barrier film and the protective film can be adjusted by the degree of crosslinking of the resins.

Examples of the crosslinking agent include isocyanate-based crosslinking agents such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and their addition products. agent; epoxy-based crosslinking agent such as ethylene glycol glycidyl ester, 1,3-bis(N,N-diglycidyl-aminomethyl)cyclohexane, etc.; hexa[1-(2-methyl)- Aziridine-based cross-linking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; chelate-based cross-linking agents such as aluminum chelates agent etc. These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferred from the viewpoints of making the adhesive layer thinner, easily lowering the adhesive force, and being easy to obtain.

The content of the crosslinking agent is appropriately adjusted according to the number of functional groups that the resin (X) has, for example, it is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the resin (X) having the above-mentioned functional groups such as the above-mentioned acrylic copolymer. parts by mass, more preferably 0.03 to 7 parts by mass, further preferably 0.05 to 4 parts by mass. When the content of the crosslinking agent is large, the crosslinking density in the adhesive layer becomes high, and the adhesive force b between the gas barrier film and the protective film tends to decrease.

(tackifier) In one aspect of the present invention, the adhesive composition may further contain a tackifier while containing the resin (X). As a tackifier, the same thing as the tackifier (E) mentioned above can be used. The content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, further preferably 0.1 to 50% by mass, and still more preferably 0.5% by mass based on the total amount of the adhesive composition. ~45% by mass, more preferably 1.0~40% by mass.

(additive for adhesive) In one aspect of the present invention, the adhesive composition may contain adhesive additives used for general adhesives other than the aforementioned tackifier and crosslinking agent within the range that does not impair the effect of the present invention. Examples of the additives for adhesives include antioxidants, softeners (plasticizers), rust inhibitors, retardants, catalysts, ultraviolet absorbers, reaction accelerators, and reaction inhibitors. In addition, these additives for adhesive agents may be used individually or in combination of 2 or more types. When these adhesive additives are contained, the content of each adhesive additive is independently preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, based on 100 parts by mass of the resin (X). .

(diluent medium) 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 above-mentioned various active ingredients, so as to 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, isopropanol, tert-butyl Alcohol, secondary butanol, acetylacetone, cyclohexanone, n-hexane, cyclohexane, etc. In addition, these diluting solvents may be used alone or in combination of two or more.

When the adhesive composition is in the form of a solution containing a diluting solvent, the active ingredient concentration of the adhesive composition is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, further preferably 10 to 50% by mass. % by mass, more preferably 25 to 45% by mass, further preferably 30 to 45% by mass.

[Peeling sheet] As the release sheet, conventionally known ones can be used. For example, the release sheet which has the release layer which peeled with the release agent on the base material for release sheets is mentioned. As the substrate for the release sheet, for example, cellophane, coated paper, Dowling paper, etc.; laminated paper made of thermoplastic resin such as polyethylene laminated on these paper substrates; polyethylene terephthalate Plastic films made of diester resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc. These can be used individually or in combination of 2 or more types. Moreover, the base material for release sheets may be the laminated body which laminated|stacked these two or more types. Examples of release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based Department of resin, etc. These can be used individually or in combination of 2 or more types.

[Manufacturing method of gas barrier laminate] The method for producing the gas-barrier laminate is not particularly limited. For example, in the method for producing an adhesive layer as described above, the adhesive layer of the protective film is attached to the gas barrier film by attaching the gas barrier film to the surface of the adhesive layer on which the release sheet is not provided. , and a gas-barrier laminate can be produced. When the protective film is a single-layer protective film, a gas barrier laminate can be produced by bonding the protective film and the gas barrier film together. For example, the protective layer can be laminated on the gas barrier film by virtue of the adhesiveness of the protective film itself.

[Seal body] The sealing body is one that seals the object to be sealed by bonding the exposed surface of the adhesive layer to the object to be sealed to cover the object to be sealed. 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 also 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 is attached so as to cover the surface of the object to be sealed and the surface of the substrate around the object to be sealed. The transparent substrate is not particularly limited, and various substrate materials can be used. It is especially preferable to use a substrate material with high visible light transmittance. Also, a material having high barrier performance against water vapor or gas penetrating from the outside of the device, and excellent solvent resistance or weather resistance is preferable. Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, etc. , polyvinylidene fluoride, cellulose acetate, brominated phenoxy, aramides, polyimides, polystyrenes, polyarylates, polysulfides, Transparent plastics such as polyolefins, etc. The thickness of the substrate is not particularly limited, and can be appropriately selected after considering the light transmittance and the performance of blocking the inside and outside of the element.

[Manufacturing method of sealing body] The method of manufacturing the sealing body is not particularly limited. For example, a sealed body is obtained by covering at least the surface of the 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 is cured by performing a curing treatment such as heating or energy ray irradiation, and thus the adhesive layer of the gas-barrier laminate is hardened. The adhesiveness of the surface of the sealing material can be further excellent. The step of peeling and removing the protective film from the gas-barrier laminate may be in any process of sealing the object to be sealed with the gas-barrier laminate to produce a sealed body, processing and transporting the sealed body. According to the gas-barrier laminate of the present invention, even if the protective film is peeled from the gas-barrier laminate at any timing, no gap is formed between the object to be sealed and the adhesive layer. Therefore, deterioration of the object to be sealed due to penetration of moisture, oxygen, or the like can be prevented. That is, in one aspect of the present invention, the method for manufacturing the sealing body preferably includes the following steps (1) to (2) in sequence. ・Step (1): The step of attaching the gas-barrier laminate of the present invention to the object to be sealed using the adhesive layer as the bonding surface ・Step (2): A step of peeling the protective film from the gas barrier laminate Also, 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 the adhesive layer is hardened, or may be performed after the adhesive layer is hardened. After hardening. When the adhesive layer is cured by heating, from the viewpoint of preventing defects caused by changes in the properties or shape of the protective layer or adhesive layer of the protective film due to the heat when the adhesive layer is hardened, the protective The step of peeling and removing the film from the gas barrier laminate is preferably before curing the adhesive layer. In addition, when the adhesive layer is cured by irradiation of energy rays, from the viewpoint of suppressing the decrease in the amount of energy rays irradiated to the adhesive layer due to the protective layer or the adhesive layer of the protective film, the protective film is removed from the gas. The step of peeling and removing the barrier laminate is preferably before hardening the adhesive layer. That is, in one aspect of the present invention, the method for manufacturing the sealing body preferably includes the following steps (1) to (3) in sequence. ・Step (1): The step of attaching the gas-barrier laminate of the present invention to the object to be sealed using the curable adhesive layer as the bonding surface ・Step (2): A step of peeling the protective film from the gas barrier laminate ・Step (3): The step of hardening the above curable adhesive layer In addition, the hardening treatment in step (3) may be heating or energy ray irradiation. Since the adhesive force a between the glass plate and the curable adhesive layer of the gas-barrier laminate of the present invention and the adhesive force b between the gas-barrier film and the protective film are adjusted to satisfy the above formula (1), even Before hardening the adhesive layer, peeling off the protective film can also prevent a gap from being generated between the object to be sealed and the adhesive layer.

The bonding conditions for bonding the adhesive layer of the gas barrier laminate to the object to be sealed are not particularly limited. The temperature during attachment is, for example, 10-60°C, preferably 20-45°C. This bonding process can be performed while applying pressure. When the adhesive layer of the gas barrier laminate is a thermosetting adhesive layer, the curing conditions when the thermosetting adhesive layer is cured are not particularly limited. For example, when the polyolefin resin (A) is an acid-modified polyolefin resin, the heating temperature is usually 80-200°C (preferably 90-150°C), and the heating time is usually 30 minutes-12 hours (preferably 1~6 hours). When the adhesive layer of the gas barrier laminate is an energy ray curable adhesive layer, the curing conditions when the energy ray curable adhesive layer is cured are not particularly limited. For example, using ultraviolet rays as energy rays, the adhesive layer can be irradiated with ultraviolet rays at an illumination intensity of 20-1000 mW/cm ² and a light intensity of 50-1000 mJ/cm ² , and the irradiation time is usually 0.1-1000 seconds, preferably 1 ~500 seconds. [Example]

The present invention will be described more specifically by the following examples, but the present invention is not limited by the following examples.

[Film thickness] (1) The thickness of the adhesion-promoting coating Measurement was performed using a film thickness measuring device (manufactured by FILMETRICS Co., Ltd., product name "F20"). (2) The thickness of the gas barrier layer Measurement was performed using a spectroscopic ellipsometer (manufactured by J.A. Woollam. Japan Co., Ltd., M-2000). (3) Determination of thickness of layers other than adhesion-promoting coating and gas barrier layer It measured using the constant-pressure thickness measuring instrument (model number: "PG-02J", standard specification: JIS K6783, Z1702, Z1709 conformity) manufactured by TECLOCK CO., LTD.

[Weight average molecular weight (Mw)] The weight average molecular weight (Mw) of the modified polyolefin resin (A1) used as the polyolefin resin (A) used as the raw material of the curable adhesive layer and the polyfunctional epoxy compound used as the curable component (B) The weight average molecular weight (Mw) of (B2), the weight average molecular weight (Mw) of the acrylic resin of the raw material of the adhesive layer which a protective film has, and the number average molecular weight (Mn) of PIB resin are the values measured using the following method.

(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 Using a gel permeation chromatography (GPC) device (manufactured by TOSOH Co., Ltd., product name "HLC-8320"), it was measured under the following conditions, and the values converted to the weight average molecular weight and number average molecular weight of standard polystyrene were used. . (measurement conditions) ・Measurement sample: tetrahydrofuran solution with a sample concentration of 1% by mass ・Column: "TSK gel Super HM-H" 2 tubes, "TSK gel Super H2000" 1 tube (both manufactured by TOSOH Co., Ltd.), connected in sequence. ・Column temperature: 40°C ・Development solvent: Tetrahydrofuran ・Flow rate: 0.60 mL/min

(2) Weight average molecular weight (Mw) of polyfunctional epoxy compound (B2) Using the above-mentioned gel permeation chromatography (GPC) device, measure under the above conditions, and convert it into the weight average of standard polystyrene corresponding to the retention time of the peak top of the peak with the largest area among the multiple peaks observed. molecular weight value.

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

(1) Preparation of gas barrier film Polyethylene terephthalate (manufactured by Toray Co., Ltd., PET50A4100, thickness 50 μm) was used as the substrate layer, and one side of the substrate layer (the smooth surface without easy-adhesive treatment) ) using a Mayer bar to coat a composition containing an ultraviolet (UV) curable resin and active silica (manufactured by JSR Co., Ltd., product name "OPSTAR Z7530") to form a coating film. Dry at 70°C for 1 minute. Then, using a conveyor-type UV light irradiation device (manufactured by Fusion Corporation, product name "F600V"), the coating film was irradiated with UV under the following conditions to harden the coating film and form an adhesion-promoting coating layer with a thickness of 1 μm. . (UV irradiation conditions) ・UV lamp: High pressure mercury lamp ・Linear velocity: 20m/min ・Integral luminous flux: 120mJ/cm ²・Illuminance: 200mW/cm ²・Lamp height: 104mm

Next, apply a coating material (manufactured by CLARIANT JAPAN Co., Ltd., trade name "AQUAMICA NL110-20") with perhydropolysilazane as its main component on the surface of the adhesion-promoting coating by spin coating, Heating at 120° C. for 1 minute to form a polysilazane layer containing perhydropolysilazane. The polysilazane layer has a thickness of 200 nm. Next, argon (Ar) plasma ions were implanted onto the surface of the polysilazane layer using a plasma ion implantation device to form a gas barrier layer, and a gas barrier film 1 having the following laminated structure was produced. (Laminate structure of gas barrier film 1) ・Substrate layer／Adhesion-promoting coating／Gas barrier layer

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

(2-1) Formation of thermosetting adhesive layer 1 100 parts by mass of polyolefin resin (A), 27 parts by mass of curable component (B), 0.1 part by mass of silane coupling agent (C), and 0.6 parts by mass of hardening catalyst (D) were dissolved in methyl ethyl ketone to Adhesive composition 1 having a solid content concentration of 20% by mass was prepared. The polyolefin resin (A) used in the preparation of the adhesive composition 1, the thermosetting component (B-1) as the curable component (B), the silane coupling agent (C) and the curing catalyst (D) are as follows Shown below. ・Polyolefin-based resin (A): manufactured by Mitsui Chemicals Co., Ltd., product name "Unistole H-200", acid-modified α-olefin polymer, solid at 25°C, weight average molecular weight (Mw) = 52,000, equivalent to Resin for modified polyolefin resin (A1). ・Thermosetting component (B-1): Mitsubishi Chemical Corporation, product name "YX8034", hydrogenated bisphenol A diglycidyl ether, liquid at 25°C, epoxy equivalent = 270g/eq, weight average molecular weight (Mw)=3,200, and it corresponds to the compound of the polyfunctional epoxy resin compound (BL) which is liquid at 25 degreeC. ・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 Chemical Industry Co., Ltd., product name "CUREZOL 2E4MZ"

The prepared adhesive composition 1 was coated on the release-treated surface of a release sheet (manufactured by Lintec Co., Ltd., trade name "SP-PET381031"), and the obtained coating film was heated at 100°C for 2 minutes to form Thermosetting adhesive layer 1 having a thickness of 10 μm.

(2-2) Formation of thermosetting adhesive layer 2 In the above "(2-1) Formation of thermosetting adhesive layer 1", the thermosetting component (B-1) was changed to the following thermosetting component (B-2) to prepare the adhesive agent composition 2 to form a thermosetting adhesive layer 2. ・Thermosetting component (B-2): Mitsubishi Chemical Corporation, product name "YX8000", hydrogenated bisphenol A diglycidyl ether, liquid at 25°C, epoxy equivalent = 205g/eq, weight average molecular weight (Mw)=1,400, and it corresponds to the compound of the polyfunctional epoxy resin compound (BL) which is liquid at 25 degreeC.

(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), 1.2 parts by mass of hardening catalyst (D), and 50 parts by mass of tackifier (E) Parts were dissolved in methyl ethyl ketone to prepare adhesive composition 3 with a solid content concentration of 28% by mass. The polyolefin-based resin (A), silane coupling agent (C), and curing catalyst (D) are the same as those used in the above-mentioned "(2-1) Formation of thermosetting adhesive layer 1". The curable component (B) is the thermosetting component (B-2) used in the aforementioned "(2-2) Formation of the thermosetting adhesive layer 2". The tackifier (E) is a copolymer of a styrene-based monomer and an aliphatic monomer (manufactured by Mitsui Chemicals Co., Ltd., product name "FTR6100", softening point=95° C.). Otherwise, the thermosetting adhesive layer 3 is formed by the same method as in the aforementioned "(2-1) Formation of the thermosetting adhesive layer 1".

(3) Preparation of protective film Prepare six types of protective films 1 to 6 described below.

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

(3-2) Preparation of protective film 2 Copolymerize 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 to prepare a (meth)acrylate copolymer (weight average molecular weight Mw=160,000) . Next, 100 parts by mass of the (meth)acrylate 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) part and 1.0 part by mass of a reaction inhibitor (acetyl acetone), were mixed, stirred well, and diluted with methyl ethyl ketone to obtain an adhesive composition with a solid content concentration of 37% by mass. This adhesive composition was coated on a release sheet (manufactured by Lintec Co., Ltd., product name "SP -PET381031", thickness: 38μm) to form a coating film on the peeled surface. This coated film was heat-treated at 90° C. for 1 minute to form an adhesive layer with a thickness of 20 μm. Thereby, the laminated body which consists of an adhesive layer and a release sheet is obtained. Next, by combining the adhesive layer of the laminate with a polyethylene terephthalate film (manufactured by Toray Advanced Materials Korea, product name "XD571S", tensile modulus of elasticity at 23°C: 3.9GPa, thickness : 38 μm) were bonded together to produce a protective film 2 having the following laminated structure. (Composition of Protective Film 2) ・Releasable sheet / Adhesive layer (thickness: 20μm, acrylic resin) / protective layer (thickness: 38μm, polyethylene terephthalate film)

(3-3) Preparation of protective film 3 The thickness of the adhesive layer of the protective film 2 was changed to 10 μm to prepare the protective film 3 . (Structure of protective film 3) ・Releasable sheet / Adhesive layer (thickness: 10μm, acrylic resin) / protective layer (thickness: 38μm, polyethylene terephthalate film)

(3-4) Preparation of protective film 4 100 parts by mass of a copolymer of isobutylene and isoprene (manufactured by Japan BUTYL Co., Ltd., product name "Exxon Butyl 268", number average molecular weight: 260,000, content of isoprene: 1.7 mol%) Acid-based functional group polyisoprene rubber (manufactured by KURARAY Co., Ltd., product name "LIR 410", number average molecular weight 30,000, average number of carboxyl groups per molecule: 10) 5 parts by mass, aliphatic petroleum resin ( Japan Zeon Co., Ltd., product name "Quintone A100", softening point 100°C) 20 parts by mass, and crosslinking agent (Mitsubishi Chemical Co., Ltd., product name "TC-5", epoxy compound) 1 part by mass It was dissolved in toluene to obtain an adhesive composition having a solid content concentration of 25% by mass. Using this adhesive composition, the protective film 4 was produced by the method similar to said "(2) protective film 2" except having adjusted the thickness of the adhesive layer to 2 micrometers. (Structure of protective film 4) ・Release sheet/adhesive layer (thickness: 2μm, PIB resin)/protective layer (thickness: 38μm, polyethylene terephthalate film)

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

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

(4) Fabrication of gas barrier laminate The gas barrier layer of the gas barrier film 1 produced in the above "(1) Formation of the gas barrier film" and the thermosetting adhesive layers 1 to 3 formed in the above "(2) Formation of the adhesive layer" fit separately. In addition, on the barrier film side (substrate layer surface), under the conditions of temperature 23°C, pressure 0.2MPa, and speed 0.2m/min, the protective film 1~ prepared in the above "(3) Preparation of protective film" 6 Laminate gas barrier film 1, thermosetting adhesive layers 1 to 3, and protective films 1 to 6 with the adhesive layer as the bonding surface, respectively, to form a gas barrier laminate of the combined laminate shown in Table 1 Body 1~18.

[Examples 1-15, Comparative Examples 1-3] For the gas barrier laminates 1 to 15 of Examples 1 to 15 and the gas barrier laminates 16 to 18 of Comparative Examples 1 to 3 shown in Table 1, the following measurements and evaluations were implemented.

(1) Determination of the adhesive force b of the protective film relative to the gas barrier film The release sheet of the gas-barrier laminate cut into a width of 50 mm and a length of 20 mm was peeled off, and the gas-barrier laminate was laminated on a soda-lime glass plate using the thermosetting adhesive layer as the bonding surface. Lamination was carried out under lamination conditions of a temperature of 23° C., a pressure of 0.2 MPa, and a speed of 2.0 m/min using a lamination device equipped with rolls (manufactured by Japan Office Laminator Co., Ltd., roll-type multilayer press). After lamination, let stand at 23°C and 50% R.H. (relative humidity) for 24 hours. Under the same environment, pull the protective film from the gas barrier film at a peeling angle of 180° to implement 180° pull-off Adhesion measurement test (N/50mm, peeling speed: 300mm/min) to measure the adhesion b between the gas barrier film and the protective film. In addition, in the appearance evaluation described later, for the case of floating, the thermosetting adhesive layer of the gas barrier laminate was attached to the soda lime glass plate through the double-sided tape and measured again to measure the adhesive force b.

(2) Appearance evaluation When measuring the adhesive force b between the gas barrier film and the protective film, it was visually checked whether or not floating was observed between the soda lime glass plate as the adherend and the thermosetting adhesive layer. The case where no floating was found was rated as "A", and the case where floating was detected was rated as "F".

(3) Measurement of the adhesive force a between the glass plate and the thermosetting adhesive layer The release sheet of the gas-barrier laminate cut into a width of 50 mm and a length of 20 mm was peeled off, and the gas-barrier laminate was laminated on a soda-lime glass plate using the thermosetting adhesive layer as the bonding surface. Lamination was carried out under lamination conditions of a temperature of 23° C., a pressure of 0.2 MPa, and a speed of 2.0 m/min using a lamination device equipped with rolls (manufactured by Japan Office Laminator Co., Ltd., roll-type multilayer press). After lamination, let it stand at 23°C and 50% R.H. (relative humidity) for 24 hours. Under the same environment, pull the gas-barrier laminate from the soda-lime glass plate at a peeling angle of 180° to implement 180°pull-off adhesion measurement test (N/50mm, peeling speed: 300mm/min), based on the adhesion a between the glass plate and the thermosetting adhesive layer.

The results are shown in Table 1.

[Table 1]

According to Table 1, it can be known as follows. As in Examples 1 to 15, it can be seen that the gas-barrier laminates with a>b have no floating and have good appearance. On the other hand, as in Comparative Examples 1 to 3, it can be seen that the gas-barrier laminates in which b>a floated and had poor appearance.

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Claims (13)

A gas-barrier laminated body comprising a laminated structure in which an adhesive layer, a gas-barrier film, and a protective film are arranged in sequence, wherein the adhesive layer is made of a polyolefin-based resin (polyolefin-based resin) (A ) layer formed of an adhesive composition, the above-mentioned adhesive layer is used as a bonding surface, and the above-mentioned gas-barrier laminate is pressed against a glass plate under the following condition (α) with a roller, and the above-mentioned gas-barrier laminate and After the above-mentioned glass plate was attached, it was peeled off under the following condition (β). Other conditions followed JIS Z0237:2000 to measure the adhesive force a between the above-mentioned glass plate and the above-mentioned adhesive layer, and the distance between the above-mentioned gas barrier film and the above-mentioned protective film. Between the adhesive force b, the above-mentioned adhesive force a and the above-mentioned adhesive force b satisfy the following formula (1), a>b. ． ． (1) Condition (α): temperature 23°C, pressure 0.2MPa, and speed 0.2m/min, condition (β): after attaching, let it stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%. The peeling speed is 300mm/min for peeling. The gas barrier laminate according to claim 1, wherein the adhesive layer is a curable adhesive layer. The gas-barrier laminate according to claim 2, wherein the polyolefin resin (A) includes a modified polyolefin resin (A1). The gas barrier laminate according to claim 2, wherein the curable adhesive layer includes a curable component (B), and the curable component (B) includes a polyfunctional epoxy resin compound that is liquid at 25°C (BL). The gas barrier laminate according to claim 4, wherein the weight average molecular weight (Mw) of the polyfunctional epoxy resin compound (BL) is 1500 to 5000. The gas barrier laminate according to claim 5, wherein the multifunctional epoxy The content of the resin compound (BL) is 10 to 34% by mass of 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 material layer and a gas barrier layer. The gas barrier laminate according to claim 7, wherein the base layer has a resin film containing one or more resin components selected from polycarbonate, cycloolefin polymer, and cycloolefin copolymer. The gas barrier laminate according to claim 7, wherein the base material layer has a thickness of 30 μm or less. The gas-barrier laminate according to claim 7, 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 claim 7, wherein the gas barrier layer and the adhesive layer are directly laminated. The gas barrier laminate according to any one of claims 1 to 6, wherein the protective film has a protective layer and an adhesive layer, and the adhesive layer is attached to the gas barrier film. A method of manufacturing a sealing body, which has the following steps (1) to (2) in sequence, step (1): using the gas barrier laminated body described in any one of Claims 1 to 12 as an adhesive layer The step of attaching the bonding surface to the object to be sealed, step (2): the step of peeling the protective film from the above-mentioned gas barrier laminate.