KR20210068018A - gas barrier laminate - Google Patents

Abstract

A gas barrier laminate having a laminate structure in which a curable adhesive layer, a gas barrier film, and a protection film are arranged in this order, wherein the gas barrier laminate is the gas barrier laminate and the curable adhesive layer is a bonding surface, The gas barrier laminate and the glass plate are affixed by pressing against a glass plate under the following condition (α) with a roller, and then peeled off under the following condition (β), and other conditions are measured in accordance with JIS Z0237: 2000, The adhesive force a between the said glass plate and the said curable adhesive bond layer, and the adhesive force b between the said gas barrier film and the said protection film, it was set as the gas barrier laminated body which satisfy|fills following formula (1). a>b ... (1) Conditions (α): temperature of 23°C, pressure of 0.2 MPa, and speed of 0.2 m/min. Conditions (β): After sticking, it was left still in an environment of 23°C and 50% of relative humidity for 24 hours. Then, peel off at a peeling rate of 300 mm/min.

Description

gas barrier laminate

The present invention relates to a gas barrier laminate.

In recent years, as a light emitting device capable of high-intensity light emission by low voltage direct current driving, an organic EL device has been attracting attention.

However, the organic EL element has a problem in that the light emitting characteristic tends to deteriorate over time. It is considered that this problem arises when oxygen, water|moisture content, etc. penetrate|invade the inside of an organic electroluminescent element, and deteriorate an electrode and an organic layer. Then, as a countermeasure against this problem, sealing an organic electroluminescent element with a sealing material, and preventing penetration of oxygen, water|moisture content, etc. is implemented.

The method of sealing to-be-sealed objects, such as an organic electroluminescent element, is specifically, proposed with the gas-barrier sealing material which has a layer structure. Patent Document 1 describes a technique for sealing an organic EL element using a sealing film in which a gas barrier film is laminated on an adhesive film.

Japanese Laid-Open Patent Publication No. 2007-197517

Like an electronic device such as an organic EL element, an object to be sealed that needs to be prevented from deterioration due to oxygen, moisture, etc. is a laminate in which an adhesive layer and a gas barrier film are laminated like the sealing film having a layer structure described in Patent Document 1 It may be sealed by the gas-barrier laminated body which has a structure.

By the way, in the process of storage and conveyance until the gas barrier laminate is used, the process of sealing the to-be-encapsulated object with the gas barrier laminate to produce an encapsulant, and in the process of processing and conveying the encapsulant, The gas barrier film is disposed on the outermost surface. Therefore, a flaw or a crack may arise in a gas barrier film, and the gas barrier property of a gas barrier film may fall. In addition, when the object to be sealed is used as a light emitting element such as an organic EL element and used for a display, etc., if a scratch or crack occurs in the gas barrier film, the scratch or crack becomes a defect, which is a factor that causes a luminescent point, etc. In some cases.

Therefore, the inventors of the present invention, the process of storage and conveyance until the gas barrier laminate is used, the process of sealing the to-be-encapsulated object with the gas barrier laminate to produce an encapsulant, and processing and conveying of the encapsulant, etc. In the process, in order to prevent the occurrence of scratches or cracks in the gas barrier film, it was considered to protect the entire surface of the gas barrier film with a protection film and peel the protection film at a desired timing. The desired timing means, for example, a timing in which the protection of the gas barrier film becomes unnecessary, a timing in which it is necessary to expose the gas barrier film, and the like.

By the way, when a to-be-sealed object is peeled off after sealing a to-be-sealed object with a gas-barrier laminated body, it became clear that a gap may arise between a to-be-sealed object and an adhesive bond layer. When a gap is generated between the object to be sealed and the adhesive layer, oxygen, moisture, or the like enters from the gap, and there is a fear that the object to be sealed may deteriorate. In addition, the appearance also deteriorates. On the other hand, in the encapsulant sealed by the gas barrier laminate, even if a gap between the encapsulated object and the adhesive layer does not occur, oxygen or moisture enters the encapsulated object due to various factors, and the encapsulation There is a possibility that the deterioration of water may occur.

The present invention has been made in view of these problems, and the process of storage and conveyance until the gas barrier laminate is used, the process of sealing the to-be-encapsulated object with the gas barrier laminate to produce an encapsulant, and the encapsulation body In the process of processing and conveying, while preventing scratches or cracks from occurring in the gas barrier film by the protection film, when the protection film is peeled off at a desired timing, a gap does not occur between the object to be sealed and the adhesive layer, Moreover, it aims at providing the gas-barrier laminated body which can make durability of a to-be-sealed object favorable, and the manufacturing method of the sealing body using this gas-barrier laminated body.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined based on the said idea that a gas barrier film was protected with a protection film. As a result, an adhesive bond layer, a gas barrier film, and a protection film make the gas barrier laminated body which has a laminated structure arrange|positioned in this order, make an adhesive bond layer a bonding surface, and stick to a glass plate under specific conditions. It discovered that the said subject was solvable by adjusting the adhesive force between a glass plate and an adhesive bond layer at the time of doing it, and the adhesive force between a gas barrier film and a protection film so that a specific relationship might be satisfied.

That is, the present invention relates to the following [1] to [14].

[1] A gas barrier laminate having a laminate structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order,

The gas barrier laminate is pressed against a glass plate under the following condition (α) with the adhesive layer as the bonding surface, and the gas barrier laminate and the glass plate are adhered, and then under the following condition (β) Peeling, and other conditions are the adhesive force a between the glass plate and the adhesive layer, and the adhesive force b between the gas barrier film and the protection film, measured in accordance with JIS Z0237:2000, the following formula (1) is satisfied which is a gas barrier laminate.

a > b ... (1)

Condition (α): temperature 23° C., pressure 0.2 MPa, and speed 0.2 m/min

Conditions (β): After sticking, it is peeled off at a peeling rate of 300 mm/min, after leaving still for 24 hours in an environment of 23°C and 50% of relative humidity.

[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 from an adhesive composition containing a polyolefin-based resin (A).

[4] The gas barrier laminate according to [3], wherein the polyolefin-based resin (A) contains a modified polyolefin-based resin (A1).

[5] [2] to [4] in which the curable adhesive layer contains a curable component (B), and the curable component (B) contains a polyfunctional epoxy compound (BL) that is liquid at 25°C The gas barrier laminate according to any one of claims.

[6] The gas barrier laminate according to [5], wherein the polyfunctional epoxy compound (BL) has a weight average molecular weight (Mw) of 1,500 or more and 5,000 or less.

[7] The gas barrier laminate according to [5] or [6], wherein the content of the polyfunctional epoxy compound (BL) is 10-34 mass% based on the total amount of the adhesive composition.

[8] The gas barrier laminate according to any one of [1] to [7], wherein the gas barrier film has a base layer and a gas barrier layer.

[9] The gas barrier laminate according to [8], wherein the base layer has a resin film containing at least one selected from polycarbonate, cycloolefin polymer, and cycloolefin copolymer as a resin component.

[10] The gas barrier laminate according to [8] or [9], wherein the thickness of the base layer is 30 µm or less.

[11] The gas barrier laminate according to any one of [8] to [10], wherein the gas barrier layer contains a polymer compound and is a modified polymer layer.

[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 protection film has a protection layer and an adhesive layer, and the adhesive layer is affixed to the gas barrier film.

[14] A method for producing a sealing body, comprising the following steps (1) to (2) in this order.

-Step (1): A step of affixing the gas barrier laminate according to any one of [1] to [13] to the object to be sealed by using the adhesive layer as the bonding surface.

-Step (2): Step of peeling the protection film from the gas barrier laminate

According to the present invention, the process such as storage and conveyance until the gas barrier laminate is used, the process of sealing the object to be sealed with the gas barrier laminate to produce an encapsulant, and the process of processing and conveying the encapsulant, etc. In this, while preventing scratches or cracks from occurring in the gas barrier film by the protection film, when the protection film is peeled off at a desired timing, a gap is not generated between the object to be sealed and the adhesive layer, and furthermore, the durability of the object to be sealed is improved. It becomes possible to provide a gas-barrier laminate that can be used as a product, and a method for producing a sealing body using the gas-barrier laminate.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent, 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 laminate structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order.

Then, the gas barrier laminate of the present invention has the gas barrier laminate as the bonding surface, and the gas barrier laminate and the glass plate are adhered to the glass plate under the following conditions (α) by pressing with a roller. Then, peeling is performed under the following conditions (β), and other conditions are the adhesive force a between the glass plate and the adhesive layer, and the adhesive force b between the gas barrier film and the protection film, measured in accordance with JIS Z0237: 2000, the following formula It is adjusted to satisfy (1).

a > b ... (1)

Condition (α): temperature 23° C., pressure 0.2 MPa, and speed 0.2 m/min

Conditions (β): After sticking, it is peeled off at a peeling rate of 300 mm/min after being left still at 23°C in an environment of 50% relative humidity for 24 hours.

In addition, in this invention, the adhesive force a between a glass plate and an adhesive bond layer peels the gas-barrier laminated body affixed on the glass plate from a glass plate, and is measured. In addition, the adhesive force b between a gas barrier film and a protection film peels a protection film from the gas barrier laminated body affixed on the glass plate, and is measured.

In addition, in this specification, a "gas barrier" means the function of preventing permeation|transmission of gases, such as oxygen and water vapor|steam.

The gas barrier laminate of the present invention will not be particularly limited as long as it has a laminate structure in which an adhesive layer, a gas barrier film, and a protection film are laminated in this order.

As a layer configuration of the gas barrier laminate of one aspect of the present invention, for example, the following aspects in which only an adhesive layer, a gas barrier film, and a protection film are laminated in this order, and further, arbitrarily laminated on an adhesive layer The following aspect which has a peeling sheet is mentioned.

・Adhesive layer/gas barrier film/protection film

· Release sheet/adhesive layer/gas barrier film/protection film

The aspect of the said laminated constitution which has a peeling sheet shows the state before using a gas-barrier laminated body as a sealing material. When using as a sealing material, a peeling sheet is peeled and removed, the surface of an exposed adhesive bond layer, and a to-be-sealed object are bonded together, and a to-be-sealed object is covered and sealed. And the removal of the protection film laminated|stacked on the gas barrier film is performed in the process of sealing a to-be-sealed object with a gas-barrier laminated body to produce a sealing body, or in processes, such as processing or conveying of the said sealing body.

Moreover, after the layer structure which the gas-barrier laminated body of this invention has is the following aspect, for example, after bonding together the surface of an exposed adhesive bond layer, and a to-be-sealed object and to cover a to-be-sealed object.

・Adhesive layer/gas barrier film/protection film

Here, the adhesive bond layer which the gas-barrier laminated body of one aspect|mode of this invention has may be a sclerosing|hardenable adhesive bond layer. In this case, after hardening a sclerosing|hardenable adhesive bond layer, the layer structure which a gas-barrier laminated body has becomes the following aspects.

・Cured adhesive layer/gas barrier film/protective film

In addition, in this invention, "curable adhesive bond layer" means an uncured adhesive bond layer.

The gas barrier film is protected by the protection film until the protection film peels off, and the gas barrier film is protected from scratches and cracks in the sealing body produced by sealing the object to be sealed with the gas barrier laminate of the present invention. occurrence is prevented.

Here, after peeling a protection film from a sealing body, it becomes the following aspects.

·Adhesive layer/gas barrier film

Moreover, after hardening the said curable adhesive bond layer when an adhesive bond layer is a sclerosing|hardenable adhesive bond layer, and after peeling a protection film from a sealing body, it becomes the following aspects.

・Cured adhesive layer/gas barrier film

In addition, in this specification, what sealed the to-be-sealed object by bonding together the surface of the exposed adhesive bond layer, and a to-be-sealed object, and covering a to-be-sealed object is called "sealing body." The adhesive layer may be non-hardened, may be hardened|cured, and the said sealing body may be in the intermediate state of non-hardening and hardening, ie, a semi-hardened state.

In addition, when the adhesive bond layer of the said sealing body is non-hardened, or when it is a semi-cured state, the said sealing body can also be called a "sealing precursor."

Moreover, in this invention, the process of hardening the adhesive bond layer of a sealing body is also included in the process of the process of a sealing body.

The present inventors, in the process of storage and conveyance until the gas barrier laminate is used, sealing the object to be sealed with the gas barrier laminate to produce an encapsulant, and in the process of processing and conveying the encapsulant, etc. Therefore, in order to prevent the occurrence of scratches or cracks in the gas barrier film, it was considered to protect the entire surface of the gas barrier film with a protection film, and to peel the protection film at a desired timing.

However, when the protective film is peeled off after the sealing object is sealed with a gas barrier laminate, a gap is generated between the sealing object and the adhesive layer, and oxygen or water vapor enters from the gap, which may cause deterioration of the sealing object. it became clear Moreover, it became clear that an external appearance became bad.

In order to elucidate this cause, the present inventors earnestly examined. As a result, it became clear that the clearance gap generate|occur|produced between a to-be-sealed object and an adhesive bond layer by the force applied when peeling a protection film.

Then, in order to solve the said problem, the present inventors conducted further earnest examination. As a result, the adhesive force a between the glass plate and the adhesive layer and the adhesive force b between the gas barrier film and the protection film when the gas barrier laminate is affixed to the glass plate under specific conditions are adjusted to satisfy the above formula (1) By doing this, it discovered that the said problem could be solved.

In this regard, the present inventors have discovered that even if the protective film is peeled off at any timing during the process of manufacturing the encapsulation body by encapsulating the encapsulated object with a gas barrier laminate, and processing and conveying the encapsulation body, the encapsulation material and the adhesive layer It was discovered that there can be provided the gas-barrier laminated body which is very easy to use in various processes without a gap|interval generate|occur|produced, and came to complete this invention.

[Physical properties of gas barrier laminate]

In the gas barrier laminate of the present invention, the gas barrier laminate has an adhesive layer as a bonding surface, is pressed against a glass plate under the following conditions (α) with a roller, and the gas barrier laminate and the glass plate are adhered , Peeling under the following conditions (β), and other conditions are the adhesive force a between the glass plate and the adhesive layer, and the adhesive force b between the gas barrier film and the protection film, measured in accordance with JIS Z0237: 2000, the following formula (1) ) is adjusted to satisfy

a > b ... (1)

Condition (α): temperature 23° C., pressure 0.2 MPa, and speed 0.2 m/min

Conditions (β): After sticking, it is peeled off at a peeling rate of 300 mm/min after being left still at 23°C in an environment of 50% relative humidity for 24 hours.

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 protection film, preferably 1.0 N/50 mm or more, more preferably 2.0 N /50 mm or more, more preferably 3 N/50 mm or more, still more preferably 4 N/50 mm or more, even more preferably 5 N/50 mm or more.

Moreover, in the gas-barrier laminate of one aspect of this invention, Although the upper limit of the adhesive force a between a glass plate and an adhesive bond layer is not specifically limited, Usually, it is 20 N/50 mm.

In the gas barrier laminate of the present invention, the adhesive force b between the gas barrier film and the protection 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 0.5 N /50 mm or more, more preferably 0.4 N/50 mm or less, still more preferably 0.3 N/50 mm or less.

Moreover, in the gas barrier laminate of one aspect of this invention, Although the lower limit of the adhesive force b between a gas barrier film and a protection film is not specifically limited, Usually, it is 0.05 N/50 mm.

Moreover, in the gas barrier laminate of one aspect of the present invention, the difference (a-b) 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 protection film is preferably 0.1 N /50 mm or more, More preferably, it is 0.3 N/50 mm or more, More preferably, it is 0.7 N/50 mm or more.

Hereinafter, with respect to the adhesive layer, the gas barrier film, and the protection film constituting the laminate structure of the gas barrier laminate of the present invention, the adhesive strength a between the glass plate and the adhesive layer and the adhesive strength b between the gas barrier film and the protection film It will be described in detail with specific methods for satisfying the above formula (1).

[Adhesive layer]

The gas barrier laminate of the present invention has an adhesive layer.

The adhesive composition constituting the adhesive layer is not particularly limited as long as the above formula (1) is satisfied, and for example, a dry-solidifying adhesive composition, a heat-melting adhesive composition, a curable adhesive composition, and a pressure-sensitive adhesive composition. An adhesive composition, etc. can be used. Specifically exemplifying the adhesive composition constituting the adhesive layer, an adhesive composition containing an acrylic resin, an adhesive composition containing a urethane resin, an adhesive composition containing a silicone resin, a rubber adhesive composition, and an adhesive composition containing a polyolefin resin , and an adhesive composition containing an epoxy resin, and the like.

These can be used individually by 1 type or in combination of 2 or more type.

Moreover, the adhesive composition may contain binder resin other than the said resin. Moreover, the adhesive composition may contain 1 or more types chosen from a sclerosing|hardenable component, a silane coupling agent, a catalyst, a polymerization initiator, a tackifier, etc.

Further, the thickness of the adhesive layer is preferably from 0.5 to 300 µm, more preferably from 3 to 200 µm, still more preferably from 5 to 150 µm, still more preferably from the viewpoint of ensuring excellent sealing properties to the object to be sealed. It is preferably 5 to 80 µm.

Further, 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 70 g/m 2 , from the viewpoint of ensuring good gas barrier properties. ·day or less.

In addition, in this specification, the "water vapor transmission rate of an adhesive layer" means a value measured using a gas transmission rate measuring device (manufactured by mocon, product name "PERMATRAN"), but a measurement value using another general-purpose water vapor transmission rate measuring device also show the same value.

Here, it is preferable that the adhesive bond layer which the gas-barrier laminated body of one aspect|mode of this invention has is a curable adhesive bond layer. Since the adhesive bond layer is curable, the adhesive bond layer is in an uncured state at the time of sticking, and while being able to stick to a to-be-sealed object easily, the followability|trackability to the unevenness|corrugation of a to-be-sealed object can also be made favorable. And by hardening, after sticking a curable adhesive bond layer to a to-be-sealed object, to-be-sealed object and an adhesive bond layer adhere|attach firmly. As a result, the gas-barrier laminate is excellent in the performance of preventing deterioration of the to-be-sealed object resulting from intrusion of oxygen, water vapor|steam, etc.

Moreover, it is preferable that the water vapor transmission rate of a sclerosing|hardenable adhesive bond layer is the same range as the "water vapor transmission rate of an adhesive bond layer" mentioned above from a viewpoint of ensuring favorable gas-barrier property. "The water vapor transmission rate of a sclerosing|hardenable adhesive bond layer" can be measured with the measuring method similar to the "water vapor transmission rate of an adhesive bond layer" mentioned above.

The curable adhesive layer is formed from a curable adhesive composition, specifically, for example, a thermosetting adhesive composition or energy ray-curable adhesive composition that can be cured by heat or energy rays.

In addition, an energy beam means what has energy proton in an electromagnetic wave or a charged particle beam, and an ultraviolet-ray, an electron beam, etc. are mentioned as an example, Preferably it is an ultraviolet-ray.

It is preferable that a curable adhesive bond layer is a thermosetting adhesive bond layer formed from a thermosetting adhesive composition.

Here, in one aspect of this invention, a curable adhesive bond layer is formed with the adhesive composition containing a curable component (B). Moreover, from a viewpoint of improving sealing performance more, it is more preferable that curable adhesive bond layer is formed with the adhesive composition containing both a polyolefin resin (A) and a sclerosing|hardenable component (B).

Moreover, one aspect of this invention WHEREIN: The adhesive composition for forming a sclerosing|hardenable adhesive bond layer may contain other components other than a polyolefin resin (A) and a sclerosing|hardenable component (B). As said other component, binder resin (A') other than polyolefin resin (A), a silane coupling agent (C), a curing catalyst (D), a cationic polymerization initiator (D'), and a tackifier (E) at least one selected from the group consisting of

In addition, in the following description, "polyolefin resin (A)", "binder resin other than polyolefin resin (A')", "curable component (B)", "silane coupling agent (C)", "curing catalyst" (D)", "cationic polymerization initiator (D')", and "tackifier (E)", respectively, "component (A)", "component (A')", "component (B)", It is also called "component (C)", "component (D)", "component (D')", and "component (E)".

In one aspect of the present invention, the total content of the components (A) and (B) in the adhesive composition containing both the polyolefin-based resin (A) and the curable component (B) is the total amount of the active ingredient in the adhesive composition. (100 mass %), preferably 70 mass % or more, more preferably 80 mass % or more, still more preferably 90 mass % or more, still more preferably 95 mass % or more, still more preferably 99 It is mass % or more, and it is 100 mass % or less normally.

Moreover, in addition to the polyolefin resin (A) and the curable component (B), an adhesive composition is 1 or more types chosen from component (A'), (C), (D), (D'), and (E). When comprising, components (A) and (B) in the adhesive composition and at least one component selected from components (A'), (C), (D), (D'), and (E) The total content is preferably 80 to 100 mass%, more preferably 85 to 100 mass%, still more preferably 90 to 100 mass%, with respect to the total amount (100 mass%) of the active ingredient of the adhesive composition, More preferably, it is 95-100 mass %.

In addition, in this specification, "the active ingredient of the adhesive composition" means the component (solid content) except the dilution solvent contained in the adhesive composition.

Hereinafter, components (A), (B), (A'), (C), (D), (D'), and (E) in an adhesive composition are demonstrated in detail.

<Polyolefin-based resin (A)>

1 aspect of this invention WHEREIN: When an adhesive bond layer is a sclerosing|hardenable adhesive bond layer, it is preferable that adhesive composition contains polyolefin resin (A).

In this specification, "polyolefin resin" means the polymer which has a repeating unit derived from an olefinic monomer.

When an adhesive composition contains polyolefin resin (A), it is easy to reduce the water vapor transmission rate of the adhesive bond layer after hardening. Therefore, it is easy to improve the water vapor barrier property of the adhesive bond layer after hardening.

The content of the polyolefin resin (A) in the adhesive composition is preferably 30 to 95 mass%, more preferably 40 to 90 mass%, further preferably 30 to 95 mass% with respect to the total amount (100 mass%) of the active ingredient of the adhesive composition. Preferably, it is 50-80 mass %.

When content of the said polyolefin resin (A) exists in the said range, it is easy to reduce the water vapor transmission rate of the adhesive bond layer after hardening more.

In addition, as the content of the polyolefin-based resin (A) in the adhesive composition increases, the adhesive strength a between the glass plate and the curable adhesive layer tends to be lowered. The adhesive strength b between the gas barrier film and the protection film is set to a value lower than the adhesive strength a. By adjusting to , the above formula (1) can be satisfied. In addition, by reducing the content of the polyolefin-based resin (A) in the adhesive composition within the range that satisfies the required water vapor barrier properties, and adjusting the adhesive force a between the glass plate and the curable adhesive layer to a value higher than the adhesive force b, the above formula (1) can be satisfied.

As an olefinic monomer which polyolefin resin (A) has, a C2-C8 alpha-olefin is preferable, Especially, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-1 -Pentene and 1-hexene are preferable.

In addition, the polyolefin resin (A) may have a unit derived from 2 or more types of (alpha)-olefin. Moreover, the polyolefin resin (A) may be a polymer which consists only of repeating units derived from an olefinic monomer, or the copolymer which consists of repeating units derived from an olefinic monomer and a monomer copolymerizable with an olefinic monomer may be sufficient. As a monomer copolymerizable with an olefinic monomer, vinyl acetate, (meth)acrylic acid ester, styrene, etc. are mentioned, for example.

In addition, in this specification, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", 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, olefinic elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, polyisobutylene, polyisoprene, etc. can be heard

These can also be used individually by 1 type or in combination of 2 or more type.

Here, in one aspect of the present invention, when the adhesive layer is a curable adhesive layer, from the viewpoint of further improving the sealing performance of the adhesive layer after curing, the polyolefin-based resin (A) is a modified polyolefin-based resin (A1) It is preferable to include

In the present specification, "modified polyolefin-based resin (A1)" means that the polyolefin-based resin (A) used as a precursor reacts with a modifier, and the functional group that the modifier has in the polyolefin-based resin (A) serving as the main chain is a side chain. introduced polymer.

Moreover, the modifier may have 2 or more types of functional groups in a molecule|numerator.

As a functional group which a modifier has as a functional group which can be introduce|transduced as a side chain into polyolefin resin (A) used as a main chain, for example, a carboxyl group, a group derived from a carboxylic acid anhydride, a carboxylate group, a hydroxyl group , epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphonic group, nitro group, urethane group, halogen atom, alkoxysilyl, etc. can be heard

Among these functional groups, a carboxyl group, a group derived from a carboxylic acid anhydride, a carboxylate ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, an isocyanate group, and an alkoxysilyl group are preferable, and among these, a group derived from a carboxylic acid anhydride desirable.

Here, the acid-modified polyolefin-based resin is preferable from the viewpoint of increasing the reactivity with the curable component (B) as the modified polyolefin-based resin (A1).

In the present specification, "acid-modified polyolefin-based resin" refers to a polyolefin-based resin (A) serving as a precursor reacts with a compound having an acid group, and an acid group is introduced into the polyolefin-based resin (A) serving as a main chain as a side chain. means polymer.

In addition, the method and conditions for introduce|transducing the acidic radical of the compound which has an acidic radical into polyolefin resin (A) used as a main chain as a side chain are not specifically limited, The introduction|transduction method of a well-known side chain is employable.

Although it will not specifically limit if it can introduce|transduce as a side chain to polyolefin resin (A) used as a principal chain as a compound which has an acidic radical, Preferably, an unsaturated carboxylic acid and its anhydride are mentioned.

Unsaturated carboxylic acids and their anhydrides include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride. , citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, and the like.

These unsaturated carboxylic acids and their anhydrides can be used individually by 1 type or in combination of 2 or more type.

Among these unsaturated carboxylic acids and its anhydrides, the viewpoint of further improving the sealing performance of the adhesive bond layer after hardening to maleic anhydride is preferable.

In addition, a commercial item may be sufficient as acid-modified polyolefin resin.

Commercially available acid-modified polyolefin-based resins include, for example, Adma (registered trademark) (manufactured by Mitsui Chemicals), Unistol (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark). (manufactured by ARKEMA), Modick (trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.

Preferably the compounding quantity of the compound which has an acidic radical to be made to react with the polyolefin resin (A) used as a precursor is 0.1-5 mass parts with respect to 100 mass parts of polyolefin resin (A) used as a precursor, More preferably, 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 acidic radical exists in the said range, it is easy to improve the sealing performance of the adhesive bond layer after hardening.

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

When the weight average molecular weight (Mw) of polyolefin resin (A) and modified polyolefin resin (A1) exists in the said range, it is easy to hold|maintain the adhesive bond layer formed from adhesive composition in a sheet form.

Further, in one aspect of the present invention, the polyolefin-based resin (A) may be composed of only the modified polyolefin-based resin (A1), or may be composed of the modified polyolefin-based resin (A1) and the non-modified polyolefin-based resin.

The content of the modified polyolefin-based resin (A1) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, still more preferably to the total amount (100% by mass) of the polyolefin-based resin (A). is 80-100 mass %, More preferably, it is 90-100 mass %.

When content of modified polyolefin resin (A1) exists in the said range, it is easy to improve the sealing performance of the adhesive bond layer after hardening more.

<Curable component (B)>

In one aspect of the present invention, when the adhesive layer is a curable adhesive layer, the adhesive composition contains a curable component (B).

In this specification, the "curable component (B)" means a component which becomes a network structure and hardens|cures in an infusible state by heating or irradiation of an energy ray etc.

When an adhesive composition contains a sclerosing|hardenable component (B), an adhesive bond layer becomes sclerosis|hardenable, and the sealing performance of the adhesive bond layer after hardening improves.

Moreover, although a thermosetting component may be sufficient as a sclerosing|hardenable component (B), and an energy-beam sclerosing|hardenable component may be sufficient, it is preferable that it is a thermosetting component.

The content of the curable component (B) in the adhesive composition is preferably 5 to 50% by mass, more preferably 5 to 48% by mass, further preferably based on the total amount (100% by mass) of the active ingredient of the adhesive composition. is 5 to 45 mass%, more preferably 10 to 40 mass%.

When content of a sclerosing|hardenable component (B) exists in the said range, it is easy to improve the sealing performance of the adhesive bond layer after hardening more.

Moreover, when an adhesive composition contains a polyolefin resin (A), content of the curable component (B) with respect to 100 mass parts of polyolefin resin (A) in an adhesive composition becomes like this. Preferably it is 5-110 mass parts. , More preferably, it is 10-100 mass parts. When the adhesive layer formed from the adhesive composition in which the content of the curable component (B) is within this range is cured, the cured adhesive layer has better water vapor barrier properties.

As a curable component (B), curable epoxy resin, a melamine resin, a urea resin, maleimide resin, etc. are mentioned, for example. These can be used individually by 1 type or in combination of 2 or more type. Among these, it is preferable that curable epoxy resin (B1) is included.

In this specification, "curable epoxy resin (B1)" means an epoxy compound which becomes a network structure and hardens|cures in an infusible state by heating or irradiation of an energy beam, etc.

Moreover, it is preferable that curable epoxy resin (B1) contains a 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.

As a polyfunctional epoxy resin (B2), the bifunctional epoxy resin which has two epoxy groups in a molecule|numerator from a viewpoint of further improving the sealing performance of the adhesive bond layer after hardening is preferable.

Examples of the bifunctional epoxy resin include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diglycidyl ether. Aromatic epoxies, such as dilether, brominated bisphenol S diglycidyl ether, and novolak-type epoxy resin (For example, phenol-novolak-type epoxy resin, cresol-novolak-type epoxy resin, brominated phenol-novolak-type epoxy resin) compound; Alicyclic epoxy compounds, such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol S diglycidyl ether; Pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2, aliphatic epoxy compounds such as 2-bis(3-glycidyl-4-glycidyloxyphenyl)propane and dimethyloltricyclodecanediglycidylether; and the like. These bifunctional epoxy resins can be used individually by 1 type or in combination of 2 or more type.

Here, in one aspect of this invention, it is preferable that the adhesive composition contains the polyfunctional epoxy compound (BL) liquid at 25 degreeC as a component (B).

In the following description, the polyfunctional epoxy compound (BL) liquid at 25 degreeC is also called "component (BL)."

A component (BL) has the effect (henceforth a "storage elastic modulus fall effect") which reduces the storage elastic modulus of an adhesive composition, when an adhesive composition becomes high temperature. For this reason, one aspect|mode of this invention WHEREIN: When an adhesive composition contains such a component (BL), the adhesive bond layer excellent in uneven trackability can be efficiently formed.

The weight average molecular weight (Mw) of the component (BL) is preferably 1,000 or more, more preferably 1,200 or more, still more preferably 1,500 or more, from the viewpoint of suppressing the generation of outgas resulting from the component (BL). , more preferably 1,800 or more, still more preferably 2,100 or more.

Moreover, the weight average molecular weight (Mw) of a component (BL) becomes like this. From a viewpoint of setting it as the adhesive composition with which the storage elastic modulus fall effect improved more, Preferably it is 5,000 or less, More preferably, it is 4,500 or less.

The adhesive force a between a glass plate and a curable adhesive bond layer changes with the magnitude|size of the weight average molecular weight (Mw) of a component (BL). Specifically, as the weight average molecular weight (Mw) of the component (BL) in the adhesive composition increases, the adhesive force a tends to decrease. By adjusting the adhesive force b between the gas barrier film and the protection film to a value lower than the adhesive force a, The above formula (1) can be satisfied. In addition, by reducing the weight average molecular weight (Mw) of the component (BL) in a range that satisfies the required outgassing suppression performance, and adjusting the adhesive force a between the glass plate and the curable adhesive layer to a value higher than the adhesive force b, Equation (1) can be satisfied.

The epoxy equivalent of component (BL) is preferably 100 to 1,500 g/eq, more preferably 150 to 1500 g/eq, still more 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 an epoxy group of 1 gram equivalent, and is a value measured based on JISK7236:2009.

The content of the component (BL) in the adhesive composition is preferably from 5 to 40% by mass, more preferably from 8 to 36% by mass, still more preferably from the total amount (100% by mass) of the active ingredient of the adhesive composition. It is 10-34 mass %.

When content of component (BL) exists in this range, generation|occurrence|production of the outgas resulting from component (BL) is also suppressed, acquiring the storage elastic modulus fall effect. The adhesive force a between a glass plate and a sclerosing|hardenable adhesive bond layer changes with the increase/decrease of content of a component (BL). When there is little content of the component (BL) in an adhesive composition, there exists a tendency for the adhesive force a to fall. In this case, the above formula (1) can be satisfied by adjusting the adhesive force b between the gas barrier film and the protection film to a value lower than the adhesive force a. Moreover, said Formula (1) can be satisfied by increasing content of the component (BL) in an adhesive composition and adjusting the adhesive force a between a glass plate and a sclerosing|hardenable adhesive bond layer to a value higher than adhesive force b.

<Binder resin (A') other than polyolefin resin (A)>

1 aspect of this invention WHEREIN: The adhesive composition may contain binder resin (A') other than polyolefin resin (A). As binder resins (A') other than polyolefin resin, a phenoxy resin, an acetal resin, etc. are mentioned.

Binder resins (A') other than polyolefin-type resin (A) may be used with polyolefin-type resin (A), and may be used instead of polyolefin-type resin (A).

<Silane coupling agent (C)>

1 aspect of this invention WHEREIN: When an adhesive bond layer is a sclerosing|hardenable adhesive bond layer, it is preferable that adhesive composition contains a silane coupling agent (C).

In this specification, "silane coupling agent (C)" means the organosilicon compound which has 2 or more types of different reactive groups in a molecule|numerator.

When an adhesive composition contains a silane coupling agent (C) further, it is easy to ensure favorable sealing performance of the adhesive bond layer after hardening also in any in normal temperature and high temperature environment. Moreover, even when an adhesive bond layer is not sclerosis|hardenability, the adhesive composition may contain the silane coupling agent (C). Also in this case, it is easy to ensure favorable sealing performance of an adhesive bond layer.

Content of the silane coupling agent in an adhesive composition is based on the whole amount (100 mass %) of an adhesive composition, Preferably it is 0.01-0.1 mass %, More preferably, it is 0.02-0.09 mass %.

Moreover, when an adhesive composition contains a polyolefin resin (A), content of the silane coupling agent (C) in an adhesive composition, with respect to 100 mass parts of polyolefin resin (A), Preferably 0.01-5.0 mass parts, More preferably, it is 0.05-1.0 mass part.

When content of a silane coupling agent (C) exists in the said range, even when it exposes for a long time in a high-temperature, high-humidity environment, it is easy to ensure favorably the sealing performance of the adhesive bond layer after hardening.

The silane coupling agent (C) is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule, from the viewpoint of making it easier to ensure better sealing performance of the adhesive layer after curing in both normal temperature and high temperature environments. .

As such a silane coupling agent, For example, polymerizable unsaturated group containing silicon compounds, such as vinyl trimethoxysilane, vinyl triethoxysilane, and methacryloxy propyl trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, etc. a silicon compound having an epoxy structure of ; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane ; 3-chloropropyltrimethoxysilane; 3-isocyanate propyltriethoxysilane; and the like. These silane coupling agents can be used individually by 1 type or in combination of 2 or more type.

<Cure catalyst (D)>

1 aspect of this invention WHEREIN: When an adhesive bond layer is a sclerosing|hardenable adhesive bond layer, it is preferable that adhesive composition contains a curing catalyst (D).

In this specification, a "curing catalyst (D)" means a catalyst which accelerates|stimulates reaction which hardens a sclerosing|hardenable component (B) with a heat|fever or an energy ray.

When an adhesive composition contains a curing catalyst (D), it is easy to improve the sealing performance at the time of the high temperature of the adhesive bond layer after hardening.

To [ content of the curing catalyst (D) made to make an adhesive composition contain in 100 mass parts of sclerosing|hardenable components (B)), Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-5 mass parts.

When content of the said curing catalyst (D) exists in the said range, it is easy to improve the sealing performance at the time of the high temperature of the adhesive bond layer after hardening more.

As the curing catalyst (D), when the curable component (B) is a thermosetting component, an imidazole-based curing catalyst which is a thermosetting curing catalyst from the viewpoint of preferably advancing curing by heating is preferable.

Examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-ethyl-4-methyl. Midazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. are mentioned. have. These imidazole-type curing catalysts can be used individually by 1 type or in combination of 2 or more type.

Among these imidazole-type curing catalysts, 2-ethyl-4-methylimidazole is preferable.

<Cathionic polymerization initiator (D')>

One aspect of this invention WHEREIN: When an adhesive bond layer is a sclerosing|hardenable adhesive bond layer, it is also preferable that adhesive composition contains a cationic polymerization initiator (D') further. Cationic polymerization initiator (D'), when an adhesive bond layer is a thermosetting adhesive bond layer, it is preferable that it is a thermal cationic polymerization initiator, When an adhesive bond layer is an energy-beam curable adhesive bond layer, it is a photocationic polymerization initiator. It is preferable to be As a thermal cationic polymerization initiator, a sulfonium salt, a quaternary ammonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned, A sulfonium salt is preferable. Examples of the photocationic polymerization initiator include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, ammonium salt compounds, antimonate compounds, diazonium salt compounds, selenium salt compounds, oxonium salt compounds, A bromine salt type compound etc. are mentioned, A sulfonium salt type compound is preferable.

When an adhesive composition contains a cationic polymerization initiator (D'), it is preferable that curable component (B) is a curable epoxy resin (B1).

<Tackifier (E)>

One aspect of this invention WHEREIN: When an adhesive bond layer is a sclerosing|hardenable adhesive bond layer, adhesive composition may contain a tackifier (E).

The tackifier (E) used in one aspect of the present invention is a component that auxiliaryly improves the adhesive properties of the curable adhesive layer, and refers to an oligomer having a weight average molecular weight (Mw) of usually less than 10,000, and a pressure-sensitive adhesive to be described later It is distinguished from resin (X) contained in a composition. Moreover, even when an adhesive bond layer is not sclerosis|hardenability, the adhesive composition may contain the tackifier (E).

Although the weight average molecular weight (Mw) of a tackifier (E) is less than 10,000 normally, Preferably it is 400-8000, More preferably, it is 500-5000, More preferably, it is 800-3500.

It is preferable to reduce content of the tackifier (E) in an adhesive composition from a viewpoint of suppressing generation|occurrence|production of the outgas resulting from a tackifier (E), and it is whole quantity (100 mass % of the active ingredient of an adhesive composition) ), Preferably it is more than 0 mass % and 30 mass % or less, More preferably, it is more than 0 mass % and 15 mass % or less, More preferably, it is 1-10 mass %. Moreover, when it is desired to suppress generation|occurrence|production of an outgas as much as possible, it is also preferable that an adhesive composition does not contain a tackifier (E).

Moreover, with respect to 100 mass parts of polyolefin resin (A) content of the tackifier (E) made to make adhesive composition contain, Preferably it is more than 0 mass parts - 80 mass parts, More preferably, it is more than 0 mass parts - It is 30 mass parts, More preferably, it is 1-20 mass parts. Moreover, when it wants to suppress generation|occurrence|production of an outgas as much as possible, as for content of a tackifier (E) with respect to 100 mass parts of polyolefin resin (A), it is preferable that there are as few as possible, and it is more preferable that it is 0 mass parts Do.

On the other hand, when there is little content of the tackifier (E) in an adhesive composition, there exists a tendency for the adhesive force a between a glass plate and a sclerosing|hardenable adhesive bond layer to fall. In this case, the above formula (1) can be satisfied by adjusting the adhesive force b between the gas barrier film and the protection film to a lower value. In addition, by increasing the content of the tackifier (E) in the adhesive composition in the range that satisfies the required outgassing suppression performance, the adhesive force a between the glass plate and the curable adhesive layer is adjusted to a higher value than the adhesive force b, The above formula (1) can be satisfied.

As a tackifier (E), For example, Rosin-type resin, such as polymerized rosin, polymerized rosin ester, and a rosin derivative; terpene-based resins such as polyterpene resins, aromatic modified terpene resins and hydrides thereof, and terpene phenol resins; coumarone indene resin; Petroleum resins, such as an aliphatic petroleum resin, an aromatic petroleum resin, its hydride, and an aliphatic/aromatic copolymer petroleum resin; styrene or substituted styrene polymers; α-methylstyrene homopolymerized resin, copolymer of α-methylstyrene and styrene, copolymer of styrene-based monomer and aliphatic monomer, copolymer of styrene-based monomer and α-methylstyrene and aliphatic monomer, and styrene-based monomer styrenic resins such as homopolymers and copolymers of styrenic monomers and aromatic monomers; and the like. These tackifiers (E) can be used individually by 1 type or in combination of 2 or more type.

Among these, as a tackifier (E), a styrenic resin is preferable and the copolymer of a styrenic monomer and an aliphatic monomer is more preferable.

The softening point of the tackifier (E) is preferably 80° C. from the viewpoint of further improving the shape retentivity of the adhesive layer to be formed and allowing the cured adhesive layer to exhibit excellent adhesive properties even in a high-temperature environment. Above, more preferably 85-170 degreeC, More preferably, it is 90-150 degreeC.

In addition, in this specification, a softening point means the value measured based on JISK5902.

When using 2 or more types of some tackifier (E), it is preferable that the weighted average of the softening point of these some tackifier belongs to the said range.

<Other additives>

One aspect of this invention WHEREIN: The adhesive composition may contain other additives other than components (A)-(E) mentioned above in the range which does not impair the effect of this invention greatly.

Although it selects suitably as another additive according to a use, For example, additives, such as a ultraviolet absorber, antistatic agent, a light stabilizer, antioxidant, resin stabilizer, a filler, a pigment, an extender, and a softener, are mentioned.

These additives can be used individually by 1 type or in combination of 2 or more type.

Moreover, even when an adhesive bond layer is not sclerosis|hardenability, the adhesive composition may contain these additives.

<Dilution solvent>

One aspect of the present invention WHEREIN: The adhesive composition may contain a dilution solvent further from a viewpoint of making the moldability of an adhesive bond layer favorable.

Although it can select suitably from organic solvent as a dilution solvent, Specifically, Aromatic hydrocarbon type solvents, such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; Ketone solvents, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; and the like.

These solvents can be used individually by 1 type or in combination of 2 or more type.

In addition, content of a solvent considers applicability|paintability etc., and is set suitably.

Moreover, even when an adhesive bond layer is not sclerosis|hardenability, the adhesive composition may contain the dilution solvent from a similar viewpoint.

<Method of Forming Adhesive Layer>

The formation method of the adhesive bond layer which comprises the gas barrier laminate of this invention is not specifically limited, A well-known method etc. are employ|adopted and can be formed suitably.

Here, in one aspect of this invention, it is preferable that an adhesive bond layer is formed from the adhesive composition mentioned above. For example, the method of apply|coating the adhesive composition mentioned above on the peeling process surface of the peeling sheet mentioned above, forming a coating film, drying the said coating film, and forming an adhesive bond layer is mentioned.

In addition, in this specification, when an adhesive bond layer is a curable adhesive bond layer, in the process of forming a curable adhesive bond layer, heat processing by heat applied when drying a coating film is included in the hardening process of a curable adhesive bond layer. doesn't happen

Examples of the method for applying the adhesive composition include a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, and a gravure coat method.

Moreover, it is preferable to add the dilution solvent mentioned above to an adhesive composition from a viewpoint of making applicability|paintability favorable, and to set it as the form of a solution.

As drying conditions at the time of drying a coating film, it is 80-130 degreeC normally, for example, Preferably it is 90-110 degreeC, and it is preferable to perform the drying process for 30 second - 5 minutes.

[Gas Barrier Film]

The gas barrier laminate of the present invention has a gas barrier film. The gas barrier film is laminated on the adhesive layer. When the gas barrier laminate of the present invention has a gas barrier film, it is possible to exhibit excellent gas barrier properties with a high effect of preventing the permeation of gases such as oxygen and water vapor.

Moreover, in the gas barrier laminated body of this invention, the protection film is laminated|stacked on the gas barrier film, and the gas barrier film is protected by the protection film. Therefore, in addition to storage and transport until use of the gas barrier laminate, the process of sealing the to-be-sealed object with the gas barrier laminate to produce a sealing body, and processing and conveying of the sealing body, etc. It is possible to prevent the gas barrier film from being scratched or cracked.

One aspect of the present invention WHEREIN: It is preferable that the gas barrier film which a gas barrier laminated body has is a film which has a base material layer at least, and has a gas barrier function. As an aspect of the said gas barrier film, what has a base material layer and a gas barrier layer is mentioned. For example, the aspect which has the following layer structure is mentioned.

・Base layer/gas barrier layer

In addition, in the aspect of the "base layer / gas barrier layer" above, in order to increase the adhesion between the base layer and the gas barrier layer, as in the following aspect, an anchor coat layer may be provided between the base layer and the gas barrier layer. .

・Base layer/anchor coat layer/gas barrier layer

In one aspect of the present invention, the gas barrier film included in the gas barrier laminate may be a single-layer resin film in which the base layer itself has a gas barrier function, and the base layer also functions as a gas barrier layer.

In one aspect of the present invention, as for the gas barrier laminate, for example, as in the following aspect, it is preferable that the gas barrier layer is disposed at a position closer to the adhesive layer than the base layer.

・Base layer/gas barrier layer/adhesive layer

Thereby, since a base material layer is not interposed between a gas barrier layer and an adhesive bond layer, the performance which a gas barrier laminated body blocks|blocks water vapor|steam improves more.

Moreover, when a gas barrier layer is a structure arrange|positioned at the position closer to an adhesive bond layer rather than a base material layer, a protection film is laminated|stacked on the base material layer of a gas barrier film. As for a base material layer, since a resin film is used so that it may mention later, the adhesiveness of a protection film and a base material layer becomes high easily. Further, even when the protection film is not directly laminated on the substrate layer, when the protection film is laminated via any organic material layer formed on the substrate layer, the adhesion between the protection film and the substrate layer tends to increase. However, since the gas barrier laminate of this invention is adjusted so that the relationship of said Formula (1) may be satisfied, when peeling a protection film, a gap does not generate|occur|produce between a to-be-sealed object and an adhesive bond layer.

In one aspect of the present invention, the water vapor transmission rate of the gas barrier film of the gas barrier laminate in an environment at a temperature of 40°C and 90% RH (relative humidity) is preferably 0.1 g/m 2 /day or less. , more preferably 0.05 g/m 2 /day or less, and still more preferably 0.005 g/m 2 /day or less.

When the water vapor transmission rate of a gas barrier film is 0.1 g/m<2>/day or less, it is easy to suppress effectively deterioration of a to-be-sealed object by using a gas-barrier laminated body. For example, it is easy to suppress the penetration|invasion of oxygen, water vapor|steam, etc. inside elements, such as an organic electroluminescent element formed on a transparent substrate, and suppress effectively that an electrode and an organic layer deteriorate.

Moreover, also about the gas barrier laminated body which has a gas barrier film and an adhesive bond layer, it is preferable that the water vapor transmission rate in the environment of a temperature of 40 degreeC and 90 %RH (relative humidity) is the same value as the above.

In addition, in this specification, "water vapor transmission rate of a gas barrier film" means a value measured using a gas transmission rate measuring apparatus (manufactured by mocon, product name "AQUATRAN 2"), but other general purpose water vapor transmission rate measuring apparatus The measurements used show the same values.

One aspect of the present invention WHEREIN: It is preferable that the gas barrier film which a gas-barrier laminated body has has optical transparency. It is preferable that the total light transmittance specifically, measured based on JISK7136:2000 is 80 % or more, It is more preferable that it is 85 % or more, It is still more preferable that it is 90 % or more. In addition, 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, and still more preferably 1 or less. .

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

<base layer>

As a base material layer which a gas barrier film has, the 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, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, Polyarylate, an acrylic resin, a cycloolefin type polymer, a cycloolefin type copolymer, an aromatic type polymer, a polyurethane type polymer, etc. are mentioned.

Among these, a polycarbonate, a cycloolefin type polymer, and a cycloolefin type copolymer are preferable from a viewpoint of setting it as a high transparency and optically isotropic gas barrier film.

In addition, these resin can be used individually by 1 type or in combination of 2 or more type. Moreover, what laminated|stacked 2 or more types of resin films may be sufficient as a base material layer.

A resin film having optical isotropy is a resin film more preferable as a constituent material of a gas barrier film when a light emitting element such as an organic EL element is used for a display purpose, but has poor flexibility and is fragile, so that it can be scratched or cracked during handling There are shortcomings that are prone to this.

In the gas barrier laminate of the present invention, as a constituent material of the gas barrier film, a resin film that is inferior in flexibility such as polycarbonate, cycloolefin-based polymer, and cycloolefin-based copolymer, and is weak, is used as a gas barrier film. Since the film is protected by the protection film, it is possible to prevent scratches or cracks from occurring in the gas barrier film during handling, and defects such as bright spots resulting from the scratches or cracks can be suppressed from occurring in the display. Therefore, in a display manufacturing process using a light emitting element, such as an organic EL element, etc., a yield can be improved.

There is no restriction|limiting in particular as for the thickness of the base material layer which a gas barrier film has, Preferably it is 0.5-500 micrometers, More preferably, it is 1-200 micrometers, More preferably, it is 5-100 micrometers.

Here, in the gas barrier laminate of the present invention, a protection film is laminated on a gas barrier film. Therefore, even when a base material layer is thin, since the thickness of a gas barrier laminated body can be ensured by a protection film, the handling property of a gas barrier laminated body can fully be ensured. Therefore, the thickness of a base material layer may generally be 30 micrometers or less which becomes difficult to ensure handling property. Therefore, 1-30 micrometers may be sufficient as the thickness of the base material layer which the gas-barrier laminated body of one aspect|mode of this invention has, 1-25 micrometers may be sufficient, and 1-20 micrometers may be sufficient as it.

<Gas barrier layer>

The gas barrier layer included in the gas barrier film is preferably a modified polymer layer containing an inorganic film and a polymer compound, from the viewpoint of reducing the thickness of the gas barrier film and having excellent gas barrier properties. And, it is more preferable that it is the said polymer layer. When the said polymeric layer is a gas barrier layer, a gas barrier layer can be made into a thing rich in flexibility, and it can be made into the thing excellent in durability with respect to the bending|flexion of a gas barrier film.

Examples of the polymer compound included in the polymer layer include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, and poly ether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and the like.

These high molecular compounds can be used individually by 1 type or in combination of 2 or more type.

Among these, from the viewpoint of forming a gas barrier layer having excellent gas barrier properties, the polymer compound contained in the polymer layer is preferably a silicon-containing polymer compound, and more preferably a polysilazane compound.

As a number average molecular weight of a polysilazane type compound, Preferably it is 100-50,000.

The polysilazane-based compound is a polymer having a repeating unit containing -Si-N- bonds (silazane bonds) in its molecule, and specifically, it is preferably a polymer having a repeating unit represented by the following general formula (I). .

[Formula 1]

In the general formula (I), n represents the number of repeating units and represents an integer of 1 or more.

Rx, Ry, and Rz are each independently a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or an alkyl represents a silyl group.

Among these, as Rx, Ry, and Rz, a hydrogen atom, a C1-C6 alkyl group, or a phenyl group is preferable, and a hydrogen atom is more preferable.

In addition, as the high molecular compound contained in the gas barrier layer, an inorganic polysilazane in which Rx, Ry, and Rz in the general formula (I) are all hydrogen atoms may be used. Organic polysilazane which is a group may be sufficient.

A polysilazane-type compound can be used individually by 1 type or in combination of 2 or more type.

Moreover, as a polysilazane type compound, a polysilazane modified material can also be used and a commercial item can also be used.

The said polymer layer may contain other components other than the polymer compound mentioned above in the range which does not impair the effect of this invention further.

As another component, a hardening|curing agent, another polymer|macromolecule, antioxidant, a light stabilizer, a flame retardant, etc. are mentioned, for example.

These can be used individually by 1 type or in combination of 2 or more type.

The content of the polymer compound in the polymer layer is preferably 50 to 100 mass% with respect to the total amount (100 mass%) of the components in the polymer layer from the viewpoint of forming a gas barrier layer having more excellent gas barrier properties, more Preferably it is 70-100 mass %, More preferably, it is 80-100 mass %.

Moreover, the thickness of the polymer layer which a gas barrier film has becomes like this. Preferably it is 50-500 nm, More preferably, it is 50-300 nm, More preferably, it is 50-200 nm.

In this invention, even if the thickness of a polymer layer is nano order, the gas-barrier laminated body which has sufficient gas-barrier property can be obtained.

As a method of forming a polymer layer, for example, a solution for forming a polymer layer containing at least one kind of polymer compound, other components as desired, and a solvent, etc. is applied to a known method such as a spin coater, a knife coater, or a gravure coater. A method of forming a coating film by coating using a used apparatus, and drying the coating film to form the coating film is exemplified.

Examples of the modification treatment of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment. Although these processes may be implemented individually by 1 type, they may be implemented in combination of 2 or more types.

The ion implantation treatment is a method of modifying the polymer layer by implanting ions into the polymer layer, as will be described later.

Plasma treatment is a method of modifying the polymer layer by exposing the polymer layer to plasma. For example, plasma processing can be performed according to the method of Unexamined-Japanese-Patent No. 2012-106421.

The ultraviolet irradiation treatment is a method of modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, according to the method of Unexamined-Japanese-Patent No. 2013-226757, an ultraviolet-ray modification process can be implemented.

Among these, from the viewpoint of efficiently reforming to the inside without roughening the surface of the polymer layer, and forming a gas barrier layer having more excellent gas barrier properties, as a modifying treatment of the polymer layer, ion implantation treatment is desirable.

Examples of ions implanted into the polymer layer during the ion implantation treatment include ions of rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; ions of alkane-based gases such as methane and ethane; ions of alkene-based gases such as ethylene and propylene; ions of alkadiene-based gases such as pentadiene and butadiene; ions of alkyne-based gases such as acetylene; ions of aromatic hydrocarbon-based gases such as benzene and toluene; ions of cycloalkane-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene; metal ions; Ion of an organosilicon compound; and the like.

These ions can be used individually by 1 type or in combination of 2 or more type.

Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable, and argon ions are more preferable from the viewpoint that ions can be implanted more easily and a gas barrier layer having particularly excellent gas barrier properties is obtained. desirable.

The method for implanting ions is not particularly limited. For example, a method of irradiating ions (ion beam) accelerated by an electric field, a method of implanting ions in plasma (ions of plasma generating gas), etc. are mentioned. A method of implanting ions is preferred.

In the method of implanting ions in plasma, for example, plasma is generated in an atmosphere containing a plasma generating gas, and a negative high voltage pulse is applied to a layer into which the ions are implanted, thereby generating ions (positive ions) in the plasma, It can be carried out by implanting into the surface portion of the ion implantation layer.

As an inorganic film used as a gas barrier layer, the film|membrane by vapor-phase film-forming of an inorganic compound or a metal is mentioned. Examples of the raw material for the film of the inorganic compound 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 oxynitrides such as silicon oxynitride; inorganic oxide carbide; inorganic nitride carbide; Inorganic oxynitride carbide etc. are mentioned.

Aluminum, magnesium, zinc, tin, etc. are mentioned as a raw material of a metal film|membrane.

These can be used individually by 1 type or in combination of 2 or more type.

Among these, an inorganic film made from an inorganic oxide, an inorganic nitride, or a metal is preferable from the viewpoint of gas barrier properties, and an inorganic film made from an inorganic oxide or an inorganic nitride as a raw material is preferable from the viewpoint of transparency. Moreover, a single layer may be sufficient as an inorganic membrane, and a multilayer may be sufficient as it.

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

As a vapor deposition method for forming an inorganic film, a PVD (physical vapor deposition) method such as a vacuum deposition method, a sputtering method, and an ion plating method, or a CVD method (chemical vapor deposition method) such as a thermal CVD method, a plasma CVD method, and an optical CVD method can be heard

<Anchor coat layer>

One aspect of this invention WHEREIN: From a viewpoint of improving more the adhesiveness of a base material layer and a gas barrier layer, you may provide an anchor-coat layer between a base material layer and a gas barrier layer.

As an anchor-coat layer, the layer which hardened the composition containing an ultraviolet curable compound is mentioned, for example. The composition containing the said ultraviolet curable compound may contain inorganic fillers, such as a silica particle.

The thickness of the anchor coat layer is preferably 0.1 to 10 µm, more preferably 0.5 to 5 µm.

[Protection Film]

The gas barrier laminate of the present invention has a protection film. A protection film is laminated|stacked on a gas barrier film, and protects a gas barrier film.

In addition, even if the protection film is peeled off at a desired timing, such as a timing when the protection of the gas barrier film becomes unnecessary or a timing when it is necessary to expose the gas barrier film, a gap is not generated between the object to be sealed and the adhesive layer, and oxygen Intrusion of moisture, etc. is prevented. In addition, it is also prevented that the appearance becomes poor.

1 aspect of this invention WHEREIN: The protection film which a gas-barrier laminated body has has a protection layer at least. As an aspect of a protection film, although a protection layer single layer may be sufficient, it is preferable that it is a laminated structure of a protection layer and an adhesive layer. By setting it as the laminated structure of a protection layer and an adhesive layer, the adhesive force of a protection film is adjusted and it is easy to obtain the gas-barrier laminated body which satisfy|fills said Formula (1).

Moreover, by having a protection film, the gas barrier laminated body of this invention can make the handling property of a gas barrier laminated body favorable, while thinning the base material layer of a gas barrier film.

In one aspect of the present invention, the total thickness of the base layer of the protection film and the gas barrier film is preferably 40 to 500 µm, more preferably 40 to 200 µm, still more preferably 50 to 150 µm.

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

<Protection layer>

As a protection layer which a protection film has, the resin film containing a resin component is preferable.

As the said resin component, the thing with high impact resistance is mentioned among the resin components mentioned as the base material layer of a gas barrier film. Examples of such a resin component include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, and polyarylay. and acrylic resins, aromatic polymers, and polyurethane polymers.

In addition, these resin can be used individually by 1 type or in combination of 2 or more type. Moreover, you may use the film which colored these. By coloring, the presence or absence of a protection film can be judged easily, and since the interface of a gas barrier film and a protection film can be made easy to recognize, when peeling a protection film, it is convenient.

The thickness of the protection layer which a protection film has should just have a thickness sufficient for protection of a gas barrier film, Preferably it is 1-500 micrometers, More preferably, it is 5-200 micrometers, More preferably, it is 10-100 micrometers.

The ratio of the thickness of the protection layer of the protection film to the thickness of the substrate layer of the gas barrier film (thickness of the protection layer/thickness of the substrate layer) is the ratio of the thickness of the substrate layer to the good handling of the gas barrier laminate while the substrate layer is thinned. From a viewpoint, Preferably it is 1-5, More preferably, it is 1.2-4.5, More preferably, it is 1.5-4.

<Adhesive layer>

The adhesive layer which a protection film has is laminated|stacked on one surface of a protection layer, and is a layer used in order to bond a protection layer and a gas barrier film together.

Here, it is preferable that the adhesive force b between a gas barrier film and a protection film is adjusted low from a viewpoint that the gas barrier laminated body of this invention satisfy|fills the relationship of said Formula (1).

The adhesive force b between a gas barrier film and a protection film can be adjusted low by making low the adhesiveness of the adhesive layer which a protection film has.

As a method of making low the adhesiveness of the adhesive layer which a protection film has, making the thickness of an adhesive layer thin, changing the kind of an adhesive layer, etc. are mentioned, for example. Moreover, the adhesive bond layer which the gas-barrier laminated body of this invention has should be provided with the characteristic required in order to seal a to-be-sealed object. Therefore, rather than changing the adhesive strength a by adjusting the kind or raw material compounding amount of the adhesive composition for forming the adhesive layer, only the sticking properties to the gas barrier film need to be controlled, the adhesive strength b by adjusting the adhesiveness of the adhesive layer It is easier to change

From a viewpoint of reducing the adhesiveness of an adhesive layer, the thickness of an adhesive layer becomes like this. Preferably they are 0.1 micrometer - 50 micrometers, More preferably, they are 0.5 micrometer - 40 micrometers, More preferably, they are 1 micrometer - 25 micrometers.

The kind of an adhesive layer can be changed by selection of resin which is a polymer contained in the adhesive composition for forming an adhesive layer. Hereinafter, the adhesive composition for forming an adhesive layer is demonstrated, examining also selection of resin which is a polymer.

<Adhesive composition>

The adhesive composition which is a forming material of an adhesive layer contains resin (X) which is a polymer.

Resin (X) itself may have adhesiveness, and does not need to have adhesiveness. When resin (X) does not have adhesiveness, you may make it the adhesive layer formed from an adhesive composition exhibit adhesiveness by adding the below-mentioned tackifier to an adhesive composition.

In addition, one aspect of this invention WHEREIN: 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, from the viewpoint of adjusting the adhesive force to a desired range, the pressure-sensitive adhesive composition may further contain one or more selected from the group consisting of a tackifier and a crosslinking agent, in addition to these, You may contain 1 or more types chosen from the group which consists of the additive for adhesives used for a dilution solvent and a general adhesive.

(Resin (X))

The weight average molecular weight (Mw) of resin (X) becomes like this. Preferably it is 10,000 or more, More preferably, it is 10,000-2 million, More preferably, it is 20,000-1,500,000.

As resin (X) contained in an adhesive composition, an acrylic resin, a urethane type resin, an olefin type resin, an acrylic urethane type resin, a polyester type resin, etc. are mentioned, for example.

These resin (X) can be used individually by 1 type or in combination of 2 or more type.

Moreover, when these resin (X) is a copolymer which has 2 or more types of structural units, the form of the said copolymer is not specifically limited, Any of a block copolymer, a random copolymer, and a graft copolymer may be sufficient.

Here, from the viewpoint of appropriately adjusting the adhesiveness of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition to lower the adhesive force b between the gas barrier film and the protection film, the resin (X) is preferably an acrylic resin or an olefinic resin, Acrylic resin is more preferable.

Content of resin (X) in an adhesive composition becomes like this in the whole amount (100 mass %) of the active ingredient of an adhesive composition, Preferably it is 30-99.99 mass %, More preferably, it is 40-99.99 mass %, More preferably, 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 this invention, acrylic resin and olefin resin preferable as resin (X) are demonstrated.

(Acrylic resin)

In one aspect of the present invention, by appropriately adjusting the adhesiveness of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive strength b between the gas barrier film and the protection film is lowered from the viewpoint of adjusting the resin (X) contained in the pressure-sensitive adhesive composition , it is preferable to include an acrylic resin.

As a content rate of the acrylic resin in resin (X), in the whole amount (100 mass %) of resin (X) contained in an adhesive composition, Preferably it is 30-100 mass %, More preferably, it is 50-100 mass %. , More preferably, it is 70-100 mass %, More preferably, it is 85-100 mass %.

As the acrylic resin usable 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, (meth) having a cyclic structure The polymer etc. which contain the structural unit derived from an acrylate are mentioned.

As a weight average molecular weight (Mw) of acrylic resin, Preferably it is 100,000-1,500,000, More preferably, it is 130,000-1.3 million.

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

As carbon number of the alkyl group which a monomer (a1') has, from a viewpoint of making it easy to adjust adhesive force low with thinning of an adhesive layer, Preferably it is 1-24, More preferably, it is 1-12.

In addition, a linear alkyl group may be sufficient as the alkyl group which a monomer (a1') has, and a branched chain alkyl group may be sufficient as it.

As the monomer (a1'), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, uryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and the like.

As the monomer (a1'), methyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is more preferable.

These monomers (a1') can be used individually by 1 type or in combination of 2 or more type.

Among these, it is preferable to use the monomer (a1') combining butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.

Moreover, these mass ratio [butyl (meth)acrylate/2-ethylhexyl (meth)acrylate] is preferably 1/9 from the viewpoint of making it easy to adjust the adhesive force b between the gas barrier film and the protection film low. to 5/5, more preferably 1/9 to 4/6, still more preferably 1/9 to 3/7.

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

The functional group of the monomer (a2') refers to a functional group that can act as a crosslinking origin or a functional group having a crosslinking promoting effect by reacting with a crosslinking agent which the pressure-sensitive adhesive composition to be described later may contain, for example, a hydroxyl group, a carboxyl group, an amino group, An epoxy group etc. are mentioned.

That is, as a monomer (a2'), a hydroxyl group containing monomer, a carboxy group containing monomer, an amino group containing monomer, an epoxy group containing monomer, etc. are mentioned, for example.

These monomers (a2') can be used individually by 1 type or in combination of 2 or more type.

As the monomer (a2'), a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable.

As a hydroxyl-containing monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate ) hydroxyalkyl (meth)acrylates such as acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Unsaturated alcohols, such as vinyl alcohol and allyl alcohol, etc. are mentioned.

As a carboxyl group containing monomer, For example, ethylenically unsaturated monocarboxylic acids, such as (meth)acrylic acid and a crotonic acid; Ethylenically unsaturated dicarboxylic acids, such as fumaric acid, itaconic acid, a maleic acid, and a citraconic acid, and its anhydride; 2-(acryloyloxy)ethyl succinate, 2-carboxyethyl (meth)acrylate, etc. are mentioned.

As a monomer (a2'), 2-hydroxyethyl (meth)acrylate is preferable.

These monomers (a2') can be used individually by 1 type or in combination of 2 or more type.

The content of the structural unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.3 to 30% by mass, still more preferably 0.5 in all the structural units (100% by mass) of the acrylic copolymer (A1). - 20 mass %, More preferably, it is 0.7-10 mass %. There exists a tendency for the adhesive force b between a gas barrier film and a protection film to become low, so that there is much content of the structural unit (a2) used as a crosslinking origin.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').

In addition, in the acrylic copolymer (A1), the content of the structural units (a1) and (a2) in the total structural units (100 mass%) of the acrylic copolymer (A1), preferably 70 to 100 mass%, More preferably, it is 80-100 mass %, More preferably, it is 85-100 mass %, More preferably, it is 90-100 mass %.

As a monomer (a3'), For example, Olefins, such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene-based monomers such as butadiene, isoprene and chloroprene; Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( (meth)acrylates having a cyclic structure such as meth)acrylate and imide (meth)acrylate; Styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, N-vinylpyrrolidone, etc. can be heard

These monomers (a3') can be used individually by 1 type or in combination of 2 or more type.

As a monomer (a3'), vinyl acetate is preferable.

(Olefin resin)

The olefin resin that can be used as the resin (X) is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.

The said olefin resin can be used individually by 1 type or in combination of 2 or more type.

Specific examples of the olefin-based resin include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, a copolymer of ethylene and propylene, a copolymer of ethylene and another α-olefin, propylene copolymers of α-olefins with other α-olefins, copolymers of ethylene and propylene with other α-olefins, copolymers of ethylene with other ethylenically unsaturated monomers (ethylene-vinyl acetate copolymer, ethylene-alkyl (meth)acrylate copolymer, ethylene-vinyl alcohol copolymer etc.) etc. are mentioned. Among these, the ethylene-vinyl acetate copolymer which is a copolymer of ethylene and another ethylenically unsaturated monomer is preferable.

In addition, as said α-olefin, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc. can be heard

As said ethylenically unsaturated monomer, vinyl acetate, an alkyl (meth)acrylate, vinyl alcohol, etc. are mentioned, for example.

The olefin-based resin may be a rubber-based resin. As a rubber-type resin which can be used as resin (X), polyisobutylene-type resin is mentioned, for example. Polyisobutylene-type resin (henceforth "PIB-type resin") will not be specifically limited if it is resin which has polyisobutylene frame|skeleton in at least one of a main chain and a side chain.

The number average molecular weight (Mn) of the PIB-based resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, still more preferably 50,000 to 800,000, still more preferably 70,000 to 600,000 All.

Examples of the PIB-based resin include polyisobutylene, which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, and a copolymer of isobutylene and butadiene. , and halogenated butyl rubber obtained by bromination or chlorination of these copolymers. Among these, the copolymer of isobutylene and isoprene is preferable.

In addition, when PIB-type resin is a copolymer, the structural unit which consists of isobutylene shall be contained most in all the structural units.

Content of the structural unit which consists of isobutylene becomes like this in all the structural units (100 mol%) of PIB-type resin, Preferably it is 80-100 mol%, More preferably, it is 90-100 mol%, More preferably, 95-mol% 100 mol%.

These PIB-type resins can be used individually by 1 type or in combination of 2 or more type.

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

(crosslinking agent)

In one aspect of the present invention, the pressure-sensitive adhesive composition, the acrylic copolymer having the above-described structural units (a1) and (a2), and the resin (X) having the above-mentioned functional group, such as a crosslinking-reactable rubber-based resin together with, further It is preferable to contain a crosslinking agent.

The said crosslinking agent reacts with the functional group which the said resin (X) has, and bridge|crosslinks resin. The adhesive force b between a gas barrier film and a protection film can be adjusted with the grade of bridge|crosslinking of resin.

As a crosslinking agent, For example, isocyanate type crosslinking agents, such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and those adducts; Epoxy-type crosslinking agents, such as ethylene glycol glycidyl ether and 1, 3-bis (N, N- diglycidyl- aminomethyl) cyclohexane; aziridine-based crosslinking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; Chelate-type crosslinking agents, such as an aluminum chelate; and the like.

These crosslinking agents can be used individually by 1 type or in combination of 2 or more type.

Among these crosslinking agents, an isocyanate type crosslinking agent is preferable from a viewpoint of making it easy to adjust adhesive force low with thinning of an adhesive layer, and easiness of availability.

The content of the crosslinking agent is appropriately adjusted depending on the number of functional groups in the resin (X), for example, with respect to 100 parts by mass of the resin (X) having the above-mentioned functional groups such as the acrylic copolymer, preferably 0.01 -10 mass parts, More preferably, it is 0.03-7 mass parts, More preferably, it is 0.05-4 mass parts. When there is much content of a crosslinking agent and the crosslinking density in an adhesive layer becomes high, there exists a tendency for the adhesive force b between a gas barrier film and a protection film to become low.

(Tackifier)

One aspect of this invention WHEREIN: The adhesive composition may contain a tackifier further with resin (X).

As a tackifier, the thing similar to the tackifier (E) mentioned above can be used.

Content of a tackifier is based on the whole quantity of an adhesive composition, Preferably it is 0.01-65 mass %, More preferably, it is 0.05-55 mass %, More preferably, it is 0.1-50 mass %, More preferably, 0.5 -45 mass %, More preferably, it is 1.0-40 mass %.

(Additive for Adhesive)

One aspect of this invention WHEREIN: The adhesive composition may contain the additive for adhesives used for general adhesives other than the tackifier and crosslinking agent mentioned above in the range which does not impair the effect of this invention.

As said additive for adhesives, antioxidant, a softener (plasticizer), a rust inhibitor, a retarder, a catalyst, a ultraviolet absorber, a reaction accelerator, reaction inhibitor etc. are mentioned, for example.

In addition, these additives for adhesives can be used individually by 1 type or in combination of 2 or more type.

When these additives for adhesives are contained, content of each additive for adhesives is each independently with respect to 100 mass parts of resin (X), Preferably it is 0.0001-20 mass parts, More preferably, it is 0.001-10 mass parts .

(dilution solvent)

In one aspect of the present invention, the pressure-sensitive adhesive composition may contain water or an organic solvent as a diluting solvent together with the various active ingredients described above, and may be in the form of a solution.

Examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, tert-butanol, s-butanol, and acetyl. Acetone, cyclohexanone, n-hexane, cyclohexane, etc. are mentioned.

In addition, these dilution solvents can be used individually by 1 type or in combination of 2 or more type.

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

[Peel Sheet]

As a release sheet, a conventionally well-known thing can be used. For example, what has the peeling layer by which the peeling process was carried out with the peeling agent on the base material for peeling sheets is mentioned.

As a base material for release sheets, For example, Paper base materials, such as glassine paper, coated paper, and high quality paper; laminated paper in which a thermoplastic resin such as polyethylene is laminated on these paper substrates; plastic film formed from polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc.; and the like.

These can be used individually by 1 type or in combination of 2 or more type. Moreover, the laminated body which laminated|stacked 2 or more types of these may be sufficient as the base material for release sheets.

Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

These can be used individually by 1 type or in combination of 2 or more type.

[Method for producing gas barrier laminate]

The manufacturing method of a gas-barrier laminated body is not specifically limited.

For example, in the manufacturing method of the adhesive bond layer demonstrated above, a gas barrier film is affixed on the surface of the adhesive bond layer in which the peeling sheet is not formed, By bonding together the adhesive layer of a protection film, and a gas barrier film, gas barrier lamination|stacking sieve can be manufactured.

When a protection film is a single|protection layer single layer, a gas barrier laminated body can be manufactured by bonding a protection layer and a gas barrier film together. For example, the protection layer can be laminated on the gas barrier film by the self-adhesiveness of the protection film.

[Envelope]

A sealing body seals a to-be-sealed object by bonding together the surface of an exposed adhesive bond layer, and a to-be-sealed object, and covering a to-be-sealed object.

As a to-be-sealed object, electronic devices, such as an organic electroluminescent element, an organic electroluminescent display element, a liquid crystal display element, a solar cell element, are mentioned, for example.

Here, the to-be-sealed object may be mounted on board|substrates, such as a transparent substrate.

When a to-be-sealed object is mounted on board|substrates, such as a transparent substrate, the curable adhesive bond layer which a gas-barrier laminate has is affixed so that the surface of a to-be-sealed object and the substrate surface around the to-be-sealed object may be covered.

The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high transmittance of visible light. In addition, a material having high barrier properties for blocking water vapor or gas from entering from outside the device and excellent solvent resistance and weather resistance is preferable.

Specifically, Transparent inorganic materials, such as quartz and glass; Polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, phenoxy bromide, aramids, polyimides, polystyrenes, polyarylates, poly Transparent plastics, such as sulfones and polyolefins; and the like.

The thickness of the transparent substrate is not particularly limited, and may be appropriately selected in consideration of the transmittance of light and the ability to block the inside and outside of the device.

[Method for manufacturing encapsulant]

The manufacturing method of the sealing body is not specifically limited. For example, a sealing body is obtained by coat|covering the surface of a to-be-sealed object at least with the adhesive bond layer of a gas-barrier laminated body. When the adhesive layer of the gas-barrier laminate is a curable adhesive layer, curing the adhesive layer of the gas-barrier laminate by curing treatment such as heating or energy ray irradiation to cure the adhesive layer on the surface of the object to be sealed. can be made more excellent. The step of peeling and removing the protective film from the gas barrier laminate may be any of a process of sealing the to-be-encapsulated object with a gas barrier laminate to produce an encapsulant, and processing and conveying of the encapsulant. . According to the gas barrier laminate of the present invention, even when the protection film is peeled from the gas barrier laminate at any timing, a gap is not generated between the object to be sealed and the adhesive layer. Therefore, deterioration of the object to be sealed due to intrusion of moisture, oxygen, or the like is prevented.

That is, in one aspect of this invention, it is preferable that the manufacturing method of a sealing body has the following processes (1)-(2) in this order.

- Process (1): The process of affixing the gas-barrier laminate of this invention to a to-be-sealed object using an adhesive bond layer as a bonding surface.

-Step (2): Step of peeling the protection film from the gas barrier laminate

Moreover, when the adhesive bond layer which a gas barrier laminated body has is a sclerosing|hardenable adhesive bond layer, the process of peeling and removing a protection film from a gas barrier laminated body may be before or after hardening of an adhesive bond layer.

In the case of curing the adhesive layer by heating, from the viewpoint of preventing problems caused by changes in the properties and shape of the protection layer and the pressure-sensitive adhesive layer of the protection film due to the heat during curing of the adhesive layer, the protection film is laminated with a gas barrier property. It is preferable that the process of peeling from a sieve and removing is before hardening an adhesive bond layer.

In addition, even when curing the adhesive layer by energy ray irradiation, from the viewpoint of suppressing a decrease in the amount of energy ray irradiated to the adhesive layer by the protection layer or the adhesive layer of the protection film, the protection film is removed from the gas barrier laminate. It is preferable that the process of peeling and removing is before hardening an adhesive bond layer.

That is, one aspect of the present invention WHEREIN: It is preferable that the manufacturing method of a sealing body has the following processes (1)-(3) in this order.

- Process (1): The process of affixing the gas-barrier laminated body of this invention to a to-be-sealed object using a curable adhesive bond layer as a bonding surface.

-Step (2): Step of peeling the protection film from the gas barrier laminate

-Step (3): Step of curing the curable adhesive layer

In addition, heating may be sufficient as the hardening process in a process (3), and energy-beam irradiation may be sufficient as it.

In the gas barrier laminate of the present invention, the adhesive force a between the glass plate and the curable adhesive layer and the adhesive force b between the gas barrier film and the protection film are adjusted to satisfy the above formula (1), so the adhesive layer is Even before hardening, a gap does not generate|occur|produce between a to-be-sealed object and an adhesive bond layer, but it is possible to peel a protection film.

The bonding conditions at the time of bonding the adhesive bond layer of a gas-barrier laminated body, and a to-be-sealed object are not specifically limited. The temperature at the time of sticking is 10-60 degreeC, for example, Preferably it is 20-45 degreeC. You may perform this bonding process, pressurizing. When the adhesive bond layer which a gas-barrier laminated body has is a thermosetting adhesive bond layer, hardening conditions at the time of hardening a thermosetting adhesive bond layer are not specifically limited. For example, when the polyolefin-based resin (A) is an acid-modified polyolefin-based resin, the heating temperature is usually 80 to 200°C (preferably 90 to 150°C), and the heating time is usually 30 minutes to 12 hours ( Preferably 1 to 6 hours).

When the adhesive bond layer which a gas-barrier laminated body has is an energy-beam curable adhesive bond layer, hardening conditions at the time of hardening an energy-beam curable adhesive bond layer are not specifically limited. For example, ultraviolet rays can be irradiated to the adhesive layer at an irradiation intensity of 20 to 1000 mW/cm 2 and a light quantity of 50 to 1000 mJ/cm 2 using ultraviolet rays as an energy ray, and the irradiation time is usually 0.1 to It is 1000 second, Preferably it is 1-500 second.

Example

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

[Thickness]

(1) Thickness of anchor coat layer

It measured using the film thickness measuring apparatus (The Filmetrics Co., Ltd. make, product name "F20").

(2) thickness of gas barrier layer

It measured using the spectroscopic ellipsometer (The J.A.Ulam Japan Co., Ltd. make, product name "M-2000").

(3) Measurement of the thickness of each layer other than the anchor coat layer and the gas barrier layer

It was measured using the static pressure thickness measuring machine manufactured by Techrock Corporation (model number: "PG-02J", standard standard: conforming to JIS K6783, Z1702, Z1709).

[Weight Average Molecular Weight (Mw)]

The weight average molecular weight (Mw) of the modified polyolefin-based resin (A1) used as the polyolefin-based resin (A), which is a raw material for the curable adhesive layer, and the weight-average molecular weight (Mw) of the polyfunctional epoxy compound (B2) used as the curable component (B) ) and the weight average molecular weight (Mw) of the acrylic resin which is a raw material of the adhesive layer which a protection film has, and the number average molecular weight (Mn) of PIB resin are the values measured with the following method.

(1) The weight average molecular weight (Mw) of the modified polyolefin resin (A1), the weight average molecular weight (Mw) of the acrylic resin, and the number average molecular weight (Mn) of the PIB resin

Using a gel permeation chromatograph (GPC) apparatus (manufactured by Tosoh Corporation, product name "HLC-8320"), it measured under the following conditions, and the value converted into the weight average molecular weight and number average molecular weight of standard polystyrene was used.

(Measuring conditions)

- Measurement sample: tetrahydrofuran solution with a sample concentration of 1% by mass

·Column: Two "TSK gel Super HM-H" and one "TSK gel Super H2000" (all manufactured by Tosoh Corporation), sequentially connected

·Column temperature: 40 ℃

·Developing solvent: tetrahydrofuran

Flow rate: 0.60 mL/min

(2) Weight average molecular weight (Mw) of polyfunctional epoxy compound (B2)

Measured under the above conditions using the above gel permeation chromatography (GPC) apparatus, and converted into the weight average molecular weight of standard polystyrene corresponding to the retention time of the peak top of the peak with the largest area among the multiple observed peaks. value was set.

[Production of gas barrier laminate]

The gas barrier film demonstrated below, the curable adhesive bond layer, and the protection film were prepared, these were laminated|stacked, and 18 types of gas-barrier laminated bodies 1-18 were produced.

(1) Preparation of gas barrier film

Polyethylene terephthalate (manufactured by Toray Corporation, PET50A4100, thickness: 50 µm) is used as a base layer, and an ultraviolet (UV) curable resin and reactive silica are placed on one side of the base layer (smooth side not treated for easy adhesion). A composition (manufactured by JSR Corporation, product name "Opstar Z7530") was applied with a Mayer bar to form a coating film, and the coating film was dried at 70°C for 1 minute. Then, using a conveyor type UV light irradiation device (manufactured by Fusion, product name “F600V”), UV was irradiated to the coating film under the following conditions to cure the coating film, and an anchor coat layer having a thickness of 1 μm was formed. .

(UV irradiation condition)

UV lamp: high pressure mercury lamp

Line speed: 20 m/min

Integrated light intensity: 120 mJ/cm2

·Irradiance: 200 mW/cm2

·Ramp height: 104 mm

Next, a coating material containing perhydropolysilazane as a main component (manufactured by Clariant Japan Co., Ltd., trade name "Aquamica NL110-20") was applied to the surface of the anchor coat layer by spin coating, followed by heating at 120° C. for 1 minute. , a polysilazane layer including perhydropolysilazane was formed. The thickness of the polysilazane layer was 200 nm.

Next, argon (Ar) was plasma ion-implanted into the surface of the polysilazane layer using a plasma ion implantation apparatus to form a gas barrier layer, and the gas barrier film 1 which has the following laminated structure was produced.

(Lamination Structure of Gas Barrier Film 1)

・Base layer/anchor coat layer/gas barrier layer

(2) Formation of adhesive layer

As an adhesive bond layer, 3 types of thermosetting adhesive bond layers 1-3 demonstrated below were formed.

(2-1) Formation of thermosetting adhesive layer 1

100 parts by mass of the polyolefin resin (A), 27 parts by mass of the curable component (B), 0.1 parts by mass of the silane coupling agent (C), and 0.6 parts by mass of the curing catalyst (D) are dissolved in methyl ethyl ketone, the solid content concentration of 20 mass% Adhesive composition 1 was prepared.

The polyolefin resin (A) used for preparation of the adhesive composition 1, the thermosetting component (B-1) used as a curable component (B), a silane coupling agent (C), and a curing catalyst (D) are shown below.

Polyolefin-based resin (A): manufactured by Mitsui Chemicals Co., Ltd., product name “Unistol H-200”, acid-modified α-olefin polymer, solid at 25°C, weight average molecular weight (Mw) = 52,000, modified polyolefin-based resin (A1) ) is a resin corresponding to

- Thermosetting component (B-1): Mitsubishi Chemical Co., Ltd. make, product name "YX8034", hydrogenated bisphenol A diglycidyl ether, 25 degreeC liquid, epoxy equivalent = 270 g/eq, weight average molecular weight (Mw) = 3,200, a compound corresponding to the polyfunctional epoxy compound (BL) which is liquid at 25 degreeC.

・Silane coupling agent (C): glycidoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name “KBM-4803”

Curing catalyst (D): 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., product name "Qazole 2E4MZ"

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

(2-2) Formation of thermosetting adhesive layer 2

In the above "(2-1) formation of thermosetting adhesive layer 1", thermosetting component (B-1) is changed to thermosetting component (B-2) shown below to prepare adhesive composition 2, , a thermosetting adhesive layer 2 was formed.

- Thermosetting component (B-2): Mitsubishi Chemical Co., Ltd. make, product name "YX8000", hydrogenated bisphenol A diglycidyl ether, liquid at 25 degreeC, epoxy equivalent = 205 g/eq, weight average molecular weight (Mw) It is a compound corresponding to the polyfunctional epoxy compound (BL) liquid at =1,400 and 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 parts by mass of silane coupling agent (C), 1.2 parts by mass of curing catalyst (D), 50 parts by mass of tackifier (E) methyl ethyl ketone was dissolved to prepare an adhesive composition 3 having a solid content concentration of 28% by mass.

The polyolefin resin (A), the silane coupling agent (C), and the curing catalyst (D) were the same as those used in the above "(2-1) formation of the thermosetting adhesive bond layer 1".

The curable component (B) was set as the thermosetting component (B-2) used in said "(2-2) formation of the thermosetting adhesive bond layer 2".

The tackifier (E) was made into the copolymer (The Mitsui Chemicals Co., Ltd. make, product name "FTR6100", softening point =95 degreeC) of a styrene-type monomer and an aliphatic monomer.

Other than that, it was carried out similarly to said "(2-1) formation of thermosetting adhesive bond layer 1", and the thermosetting adhesive bond layer 3 was formed.

(3) Preparation of protection film

Six types of protection films 1 to 6 described below were prepared.

(3-1) Preparation of protection film 1

A polyethylene-based film (manufactured by San-A-Hwayeon Co., Ltd., product name "PAC-3-70") was used as the protection film 1.

(Configuration of Protect Film 1)

·Adhesive layer (ethylene-vinyl alcohol copolymer)/protective layer (low density polyethylene film)

(3-2) Preparation of Protect Film 2

20 mass parts of n-butyl acrylate, 80 mass parts of acrylic acid 2-ethylhexyl, and 2.5 mass parts of acrylic acid 2-hydroxyethyl were copolymerized, and the (meth)acrylic acid ester copolymer (weight average molecular weight Mw=160,000) was prepared.

Next, 100 parts by mass of the (meth)acrylic acid ester copolymer, 3.4 parts by mass of an isocyanate-based crosslinking agent (hexamethylene diisocyanate), 0.010 parts by mass of a reaction accelerator (dioctyltin dilaurate), and a reaction inhibitor (acetylacetone) ) 1.0 mass part was mixed, it fully stirred, and it diluted with methyl ethyl ketone, and obtained the adhesive composition of 37 mass % of solid content concentration.

The pressure-sensitive adhesive composition was applied with a knife coater on the peeling surface of a release sheet (manufactured by Lintec Co., Ltd., product name "SP-PET381031", thickness: 38 µm) in which one side of a polyethylene terephthalate film was peeled off with a silicone release agent. A film was formed. The said coating film was heat-processed at 90 degreeC for 1 minute, and the 20-micrometer-thick adhesive layer was formed. Thereby, the laminated body which consists of an adhesive layer and a peeling sheet was obtained.

Next, by bonding the pressure-sensitive adhesive layer of the laminate and one side of a polyethylene terephthalate film (manufactured by Toray Advanced Materials Korea, product name "XD571S", tensile modulus at 23°C: 3.9 GPa, thickness: 38 µm), the following A protective film 2 having a laminated structure of

(Configuration of Protect Film 2)

Release sheet/adhesive layer (thickness: 20 μm, acrylic resin)/protection layer (thickness: 38 μm, polyethylene terephthalate film)

(3-3) Preparation of Protect Film 3

The thickness of the adhesive layer of the protection film 2 was changed into 10 micrometers, and the protection film 3 was produced.

(Configuration of Protect Film 3)

Release sheet/adhesive layer (thickness: 10 μm, acrylic resin)/protection layer (thickness: 38 μm, polyethylene terephthalate film)

(3-4) Preparation of protection film 4

100 parts by mass of a copolymer of isobutylene and isoprene (manufactured by Nippon Butyl Co., Ltd., product name "Exxon Butyl 268", number average molecular weight 260,000, isoprene content: 1.7 mol%) and polyisoprene rubber having a carboxylic acid-based functional group (Co., Ltd.) Kuraray, product name "LIR410", number average molecular weight 30,000, average number of carboxyl groups per molecule: 10) 5 parts by mass, and aliphatic petroleum resin (manufactured by Nippon Xeon Co., Ltd., product name "Qinton A100", softening point 100°C) 20 mass Part and 1 mass part of a crosslinking agent (The Mitsubishi Chemical Corporation make, product name "TC-5", an epoxy compound) were melt|dissolved in toluene, and the adhesive composition of 25 mass % of solid content concentration was obtained.

The protection film 4 was produced by the method similar to said "(2) protection film 2" except having adjusted the thickness of an adhesive layer to 2 micrometers using the said adhesive composition.

(Composition of Protect Film 4)

Release sheet/adhesive layer (thickness: 2 μm, PIB resin)/protective layer (thickness: 38 μm, polyethylene terephthalate film)

(3-5) Preparation of protection film 5

The thickness of the adhesive layer of the protection film 4 was changed into 10 micrometers, and the protection film 5 was produced.

(Configuration of Protect Film 5)

Release sheet/adhesive layer (thickness: 10 μm, PIB resin)/protection layer (thickness: 38 μm, polyethylene terephthalate film)

(3-6) Preparation of protection film 6

A weakly adhesive adhesive sheet (manufactured by Lintec Co., Ltd., product name "PF-PET38C") was used as the protection film 6.

(Composition of Protect Film 6)

·Adhesive layer (acrylic resin)/protective layer (polyethylene terephthalate film)

(4) Preparation of gas barrier laminate

The gas barrier layer of the gas barrier film 1 produced in the above "(1) preparation of a gas barrier film" and the thermosetting adhesive bond layers 1 to 3 formed in the above "(2) formation of an adhesive bond layer", respectively pasted together. Then, on the barrier film side (substrate layer surface), under the conditions of a temperature of 23° C., a pressure of 0.2 MPa, and a speed of 0.2 m/min, the protection films 1 to 6 prepared in the above “(3) Preparation of a protection film”, Gas barrier laminates 1 to 18 in which the pressure-sensitive adhesive layer was laminated as a bonding surface, respectively, and the gas barrier film 1, the thermosetting adhesive layers 1 to 3, and the protection films 1 to 6 were laminated in a combination shown in Table 1 produced.

[Examples 1 to 15, Comparative Examples 1 to 3]

The following measurement and evaluation were performed about the gas barrier laminated bodies 1-15 of Examples 1-15 shown in Table 1, and the gas barrier laminated bodies 16-18 of Comparative Examples 1-3.

(1) Measurement of the adhesive force b of the protection film to the gas barrier film

The release sheet of the gas barrier laminate cut to 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. For lamination, a lamination apparatus provided with a roller (manufactured by Nippon Office Laminator, roll type multi-laminator) was used, and lamination conditions were a temperature of 23°C, a pressure of 0.2 MPa, and a speed of 2.0 m/min.

After lamination, at 23°C, 50% R.H. (Relative humidity) for 24 hours, and under the same environment, at a peeling angle of 180°, the protective film was peeled from the gas barrier film, and 180° peeling adhesion measurement test (N/50 mm, peeling rate: 300 mm/ min) to measure the adhesive force b between the gas barrier film and the protection film. In addition, in appearance evaluation mentioned later, about the thing which floatation generate|occur|produced, the thermosetting adhesive bond layer of a gas barrier laminated body was affixed to a soda-lime glass plate via a double-sided tape, and it measured again, and the adhesive force b was measured.

(2) Appearance evaluation

At the time of measuring the adhesive force b between the gas barrier film and the protection film, it was visually confirmed whether floating was not seen between the soda-lime glass plate as an adherend and the thermosetting adhesive layer. The case where floatation was not seen was made into "A", and the case where floatation occurred was made into "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 to 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. For lamination, a lamination apparatus provided with a roller (manufactured by Nippon Office Laminator, roll type multi-laminator) was used, and lamination conditions were a temperature of 23°C, a pressure of 0.2 MPa, and a speed of 2.0 m/min.

After lamination, at 23°C, 50% R.H. (relative humidity) for 24 hours, and under the same environment, at a peel angle of 180°, the gas barrier laminate was peeled from a soda lime glass plate, and 180° peel adhesion measurement test (N/50 mm, peeling rate: 300 mm/min), and the adhesive force a between a glass plate and a thermosetting adhesive bond layer was measured.

A result is shown in Table 1.

Table 1 shows the following.

As in Examples 1 to 15, it turns out that the gas-barrier laminated body of a>b does not show floating, but an external appearance is favorable.

On the other hand, as in Comparative Examples 1-3, it turns out that the gas-barrier laminated body of a<b is floated and becomes an appearance defect.

Claims (14)

A gas barrier laminate having a laminate structure in which an adhesive layer, a gas barrier film, and a protection film are arranged in this order,
The gas barrier laminate is pressed against a glass plate under the following conditions (α) with the adhesive layer as a bonding surface, and the gas barrier laminate and the glass plate are adhered, followed by The adhesive force a between the glass plate and the adhesive layer, and the adhesive force b between the gas barrier film and the protection film, measured in accordance with JIS Z0237:2000, and the adhesive force b between the gas barrier film and the protection film, are the following formula A gas barrier laminate that satisfies (1).
a > b ... (1)
Condition (α): temperature 23° C., pressure 0.2 MPa, and speed 0.2 m/min
Conditions (β): After sticking, it is peeled off at a peeling rate of 300 mm/min, after leaving still for 24 hours in an environment of 23°C and 50% of relative humidity The method of claim 1,
The gas barrier laminate, wherein the adhesive layer is a curable adhesive layer. 3. The method of claim 2,
The said adhesive bond layer is a layer formed from the adhesive composition containing polyolefin resin (A), The gas-barrier laminated body. 4. The method of claim 3,
The gas barrier laminate in which the said polyolefin resin (A) contains a modified polyolefin resin (A1). 5. The method according to any one of claims 2 to 4,
The said curable adhesive bond layer contains a sclerosing|hardenable component (B), The gas-barrier laminated body in which the said curable component (B) contains a liquid polyfunctional epoxy compound (BL) at 25 degreeC. 6. The method of claim 5,
The gas barrier laminated body whose weight average molecular weights (Mw) of the said polyfunctional epoxy compound (BL) are 1,500 or more and 5,000 or less. 7. The method according to claim 5 or 6,
The gas barrier laminate whose content of the said polyfunctional epoxy compound (BL) is 10-34 mass % based on the whole quantity of adhesive composition. 8. The method according to any one of claims 1 to 7,
The gas barrier laminate in which the said gas barrier film has a base material layer and a gas barrier layer. 9. The method of claim 8,
The gas barrier laminate in which the said base material layer has a resin film containing 1 or more types selected from polycarbonate, a cycloolefin polymer, and a cycloolefin copolymer as a resin component. 10. The method according to claim 8 or 9,
The thickness of the said base material layer is 30 micrometers or less, The gas-barrier laminated body. 11. The method according to any one of claims 8 to 10,
The gas barrier laminate, wherein the gas barrier layer is a polymer layer containing a polymer compound and subjected to a modification treatment. 12. The method according to any one of claims 8 to 11,
A gas barrier laminate, wherein the gas barrier layer and the adhesive layer are directly laminated. 13. The method according to any one of claims 1 to 12,
The gas barrier laminate in which the said protection film has a protection layer and an adhesive layer, and the said adhesive layer is affixed to the said gas barrier film. The manufacturing method of the sealing body which has following process (1)-(2) in this order.
- Process (1): The process of affixing the gas-barrier laminated body in any one of Claims 1-13 to a to-be-sealed object using an adhesive bond layer as a bonding surface.
-Step (2): Step of peeling the protection film from the gas barrier laminate