TWI772392B - Gas barrier film and sealing body - Google Patents

Abstract

The gas-barrier film of the present invention is a gas-barrier film having a laminate formed by laminating a release sheet, a base layer, a gas-barrier layer, and an adhesive layer in this order, and the adhesive layer is composed of a polyolefin-based resin (A ) and the layer formed of the adhesive composition of the thermosetting component (B).

Description

Gas barrier film and sealing body

The present invention relates to a gas-barrier film and a sealed body in which the gas-barrier film and the object to be sealed are sealed with the gas-barrier film.

In recent years, an organic EL element has been attracting attention as a light-emitting element capable of high-luminance light emission by low-voltage DC driving. However, in the organic EL element, there is a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are likely to decrease with the passage of time. The problem of performance degradation over time represented by organic EL elements is generally applicable to electronic components or optical components that have attracted attention in recent years. For this reason, it is considered that oxygen, moisture, or the like is infiltrated into the interior of the electronic member or the optical member, and the performance deteriorates. In addition, as a solution to this reason, several methods have been proposed for sealing electronic components, optical components, etc., which are objects to be sealed, with a sealing material having a gas-barrier property composed of layers.

For example, Patent Document 1 discloses a gas-barrier adhesive sheet having a layer structure of release sheet/protective layer/gas barrier layer/adhesive layer/release sheet as a sealing material. The invention of the gas-barrier adhesive sheet having such a configuration is based on the idea of providing a laminate for transfer having a gas-barrier layer (paragraph 0004 of Patent Document 1). That is, if it is a laminate for transfer, since the adhesive layer is attached to the object to be sealed, and then the release sheet is removed, until the gas barrier member is applied to the object to be sealed, the release sheet functions as the support, because The protective layer does not need to function as a support, so the choice of the material of the protective layer is wide. In such a laminate for transfer, although an adhesive layer or an adhesive layer is indispensable, Patent Document 1 describes acrylic adhesives, rubber-based adhesives, polyurethane adhesives as adhesives for forming the adhesive layer. Ester-based adhesive, polysiloxane-based adhesive.

In addition, Patent Document 2 discloses that a gas barrier film having a layered structure of a cured resin layer/gas barrier layer/adhesive layer is used as a sealing material. The invention of Patent Document 2 is also disclosed in the form of a sheet in the curing resin layer lamination step (refer to paragraph 0138 of Patent Document 2), and the gas barrier film at this time can be used as a laminate for transfer as in Patent Document 1. The gas barrier film using the cured resin layer of the invention of Patent Document 2 is excellent in heat resistance, solvent resistance, interlayer adhesion, gas barrier properties, low birefringence, and excellent optical isotropy (Patent Document 2 paragraph 0007). In Patent Document 2, as a material for forming the adhesive layer, adhesives or adhesives such as acrylic, polysiloxane, and rubber are described. [Prior Art Literature] [Patent Literature]

[Patent Document 1] WO2013/018602 No. [Patent Document 2] WO2013/065812 No.

[The problem to be solved by the invention]

With the sealing materials disclosed in Patent Document 1 and Patent Document 2, although the advantage of the form of the so-called laminate for transfer is considered, in the long run, it is necessary to maintain the excellent sealing performance to the object to be sealed (prevention of external influences). The effect leads to the performance of damage to the sealed object), and there is still room for improvement.

Therefore, the present invention has been accomplished in order to solve the above-mentioned problems, and provides a gas barrier film in the form of a laminate for transfer, which properly maintains the original performance of the object to be sealed in the long run, and provides a sealing performance for the object to be sealed. An excellent gas-barrier film is also intended to provide a sealing body in which a to-be-sealed object is sealed with the gas-barrier film. [means to solve the problem]

As a result of diligent research in view of the above-mentioned problems, the present inventors have found that by forming the adhesive layer from an adhesive composition containing a polyolefin-based resin (A) and a thermosetting component (B), it is possible to properly maintain the adhesive layer over a long period of time. The initial performance of the sealing material is excellent for the sealing performance of the sealed material, and finally the present invention is completed. That is, the present invention is as follows.

[1] A gas-barrier film comprising a laminate formed by laminating a release sheet, a base layer, a gas-barrier layer, and an adhesive layer in this order, wherein the adhesive layer is composed of A layer formed of an adhesive composition containing a polyolefin-based resin (A) and a thermosetting component (B). [2] The gas barrier film according to the above [1], wherein the polyolefin-based resin (A) contains a modified polyolefin-based resin (A1). [3] The gas barrier film according to the above [1] or [2], wherein the thermosetting component (B) contains a thermosetting epoxy resin (B1). [4] The gas barrier film according to any one of the above [1] to [3], wherein the adhesive layer is directly laminated on the gas barrier layer. [5] The gas barrier film according to any one of the above [1] to [4], wherein the adhesive layer is formed by laminating the gas barrier layer through an adhesion enhancing layer. [6] The gas barrier film according to any one of the above [1] to [5], wherein the base layer is a layer formed of a composition for a base layer containing an energy ray curable component. [7] The gas barrier film according to any one of the above [1] to [6], wherein the base layer is a layer formed of a base layer composition further containing a thermoplastic resin. [8] The gas barrier film according to the aforementioned [7], wherein the glass transition temperature (Tg) of the thermoplastic resin is 140°C or higher. [9] The gas barrier film according to any one of the above [1] to [8], wherein the thickness of the base layer is 0.1 to 10 μm. [10] The gas-barrier film according to any one of [1] to [9], wherein the gas-barrier layer contains a polysilazane-based compound and is formed by performing a modification treatment. [11] A sealing body, wherein a to-be-sealed object is sealed with the gas-barrier film according to any one of the aforementioned [1] to [10], and the to-be-sealed object is selected from an organic EL element and an organic EL display element , at least one of the group consisting of inorganic EL elements, inorganic EL display elements, electronic paper elements, liquid crystal display elements and solar cell elements. [12] A method for producing a sealing body, comprising the step of adhering the adhesive layer possessed by the gas barrier film according to any one of claims 1 to 10 to an object to be sealed, and the steps of attaching the adhesive layer to the object to be sealed, and removing the gas barrier film from the above-mentioned gas barrier film. The steps of peeling off the aforementioned peeling sheets. [Effect of invention]

According to the present invention, with respect to the gas barrier film which is the form of the laminate for transfer, it is possible to provide a gas barrier film which properly maintains the original performance of the object to be sealed and has excellent sealing performance against the object to be sealed in the long run. At the same time, a sealing body in which a sealed object is sealed with the gas barrier film can be provided.

[Gas-barrier film] The gas-barrier film of the present invention has a laminate formed by laminating a release sheet, a base layer, a gas-barrier layer and an adhesive layer in this order, and the adhesive layer is composed of a polyolefin-based resin containing a (A) and the layer formed of the adhesive composition of the thermosetting component (B). In addition, the so-called "gas barrier property" here refers to the property of preventing the permeation of gases such as oxygen or water vapor.

Although the gas barrier film of the present invention is formed by laminating a release sheet, a base layer, a gas barrier layer and an adhesive layer in this order, it is not particularly limited, but the adhesive layer can be directly laminated on the gas barrier layer , and can also be laminated on the gas barrier layer through the adhesion enhancement layer.

As a layer structure which the gas-barrier film of this invention has, for example, the aspect shown below which has the 2nd release sheet which is laminated|stacked on the adhesive agent layer at will is mentioned. ‧First release sheet/base layer/gas barrier layer/adhesive layer/second release sheet In the aspect of the layer structure, the so-called first release sheet and the second release sheet may be the same or different. When the above-mentioned layer structure is used in the state before the gas barrier film is used as a sealing material, the second release sheet is usually peeled off, and the exposed adhesive layer is bonded to the object to be sealed, and then the second release sheet is removed. A sealed body is obtained. In addition, after bonding the surface of the adhesive layer of the sealing material to the surface of the object to be sealed, the first release sheet is usually peeled off to expose the resin layer, and the layer structure shown below can be obtained. ‧Substrate layer/gas barrier layer/adhesive layer ‧Substrate layer/gas barrier layer/adhesion enhancement layer/adhesive layer Even if the gas barrier film of the present invention does not have a substrate, the first release sheet is removed from the first release sheet. During this time, it functions as a support or a protective member for the gas barrier film.

[Laminate] The lamination system of the present invention is constituted by laminating a release sheet, a base layer, a gas barrier layer, and an adhesive layer in this order, and the adhesive layer is composed of a polyolefin-based resin (A) and a thermosetting component ( The adhesive composition of B) is formed. The water vapor transmission rate of the laminate constituting the gas barrier film of the present invention is preferably 5.0 g/m ² /day or less, more preferably 0.5 g/m ² /day or less, still more preferably 5×10 ⁻² ( g/m ² /day) or less, still more preferably 5×10 ^-3 (g/m ² /day) or less. In the present invention, a gas barrier film having a high effect of preventing the permeation of gases such as oxygen and water vapor and having excellent gas barrier properties can be obtained because the water vapor transmission rate of the laminate is in the above range. The term "water vapor transmission rate" here refers to the value measured in a high temperature and high humidity environment of 40°C and a relative humidity of 90% using a water vapor transmission rate measuring device, but the more specific measurement method is based on the following Methods of Examples. Furthermore, although the gas barrier film of the present invention is preferably used to peel off the first release sheet after the object to be sealed, the water vapor transmission rate of the release sheet is usually very high compared with the water vapor transmission rate of the gas barrier layer. Therefore, it is considered that the water vapor transmission rate of the laminate measured by directly remaining the first release sheet reflects the gas barrier performance of the film-like body formed on the object to be sealed by removing the first release sheet from the laminate. Therefore, the water vapor transmission rate of the gas barrier film of the present invention is the value measured by directly remaining the first release sheet in order to maintain the autonomy of the gas barrier film as shown in the examples described later.

[Adhesive Layer] The inventors of the present invention used a gas-barrier film having a normal adhesive layer as a sealing material, and as an accelerated test, a sealed body obtained by sealing a to-be-sealed object with this sealing material was subjected to a high temperature and high humidity environment When exposed for a long period of time, it has been observed that the original properties of the sealed object are deteriorated. This reason is considered to be due to the decrease in the adhesion between the adhesive layer of the sealing material and the bonding surface of the object to be sealed, partial peeling occurs between the adhesive layer of the sealing material and the object to be sealed, and the gap between the partial peeling is intruded. Gases such as oxygen or water vapor have adverse effects on the object to be sealed. Therefore, the inventors of the present invention have studied materials for forming an adhesive layer that have a small decrease in the adhesiveness between the adhesive layer of the sealing material and the adhesive surface of the object to be sealed in the long term and have excellent adhesive strength. As a result of repeated studies by the present inventors, it has been found that by forming the adhesive layer from the adhesive composition containing the polyolefin-based resin (A) and the thermosetting component (B), the adhesive layer of the sealing material has a long-term effect on the adhesive layer of the sealing material. Excellent adhesion is maintained with the bonding surface of the object to be sealed.

The thickness of the adhesive layer is preferably 0.5-300 μm, more preferably 3-200 μm, still more preferably 5-150 μm, still more preferably 5-80 μm. When the thickness of the above-mentioned adhesive layer is in the above-mentioned range, it becomes easy to use suitably when using the gas-barrier film as a sealing material.

(Adhesive composition) The adhesive layer of the present invention is formed from an adhesive composition containing a polyolefin-based resin (A) and a thermosetting component (B). In this way, the water vapor barrier property of the adhesive layer can be improved, and the sealing performance can be improved, and at the same time, excellent bonding strength can be obtained on the bonding surface of the adhesive layer of the sealing material and the object to be sealed, and further, the adhesive layer of the sealing material and the bonding surface of the object to be sealed can be obtained. The adhesive surface of the object to be sealed maintains excellent adhesiveness for a long period of time. Therefore, it is suitable to maintain the original performance of the object to be sealed, and to obtain a gas barrier film excellent in sealing performance to the object to be sealed. Hereinafter, each component contained in an adhesive composition suitable as a material for forming an adhesive layer will be described.

<Polyolefin-based resin (A)> The adhesive composition of the present invention contains a polyolefin-based resin (A). As a result, the water vapor transmission rate of the adhesive layer is reduced, and the gas barrier film system has excellent moisture barrier properties. The term "polyolefin-based resin" as used herein refers to a polymer having repeating units derived from olefin-based monomers.

The olefin-based monomer is preferably an α-olefin having 2 to 8 carbon atoms, and among them, ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene. Furthermore, the polyolefin-based resin may have two or more units derived from α-olefins. In addition, the polyolefin-based resin may be a polymer composed only of repeating units derived from olefin-based monomers, or may be polymers composed of repeating units derived from olefin-based monomers and those derived from copolymerizable olefin-based monomers. A polymer composed of repeating units of monomers. As a monomer which can be copolymerized with an olefin type monomer, vinyl acetate, (meth)acrylate, styrene, etc. are mentioned, for example.

Examples of the polyolefin-based resin (A) include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and linear low density polyethylene. Polyethylene, polypropylene (PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(methyl) Acrylate copolymer, polyisobutylene, polyisoprene, etc.

As the above-mentioned polyolefin-based resin (A), it is preferable to contain a modified polyolefin-based resin (A1). Thereby, the adhesive layer is further excellent in adhesive strength. The term "modified polyolefin-based resin (A1)" as used herein means that the polyolefin-based resin (A) as a precursor reacts with a modifier, and the polyolefin-based resin (A) as the main chain acts as a side chain A polymer into which functional groups possessed by a modifier are introduced. Furthermore, the modifier can have two or more functional groups in the molecule.

As a functional group possessed by the modifier and a functional group which can be introduced as a side chain in the polyolefin-based resin (A) serving as the main chain, for example, a carboxyl group, a group derived from a carboxylic acid anhydride, a carboxylate group, and a hydroxyl group are exemplified. , epoxy group, amide group, ammonium group, nitrile group, amine group, amide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, phosphonium group, phosphino group (Phosphono) , nitro, urethane group, halogen atom, alkoxysilyl group, etc. Among these functional groups, carboxyl groups, groups derived from carboxylic acid anhydrides, carboxylate ester groups, hydroxyl groups, ammonium groups, amino groups, imide groups, isocyanate groups, and alkoxysilyl groups are preferred, and among them, preferred Radical derived from carboxylic acid anhydride.

(Acid-modified polyolefin-based resin) Examples of the modified polyolefin-based resin include acid-modified polyolefin-based resins and silane-modified polyolefin-based resins. Among these, acid-modified polyolefin-based resins are preferred from the viewpoint of high reactivity with the thermosetting component (B).

The term "acid-modified polyolefin-based resin" as used herein means that the polyolefin-based resin (A) as a precursor reacts with a compound having an acid group, and the polyolefin-based resin (A) as the main chain acts as a side chain Polymers that introduce acid groups. Furthermore, as the method and conditions for introducing the acid group of the compound having an acid group as the side chain of the polyolefin-based resin (A) as the main chain, a known method for introducing the side chain can be adopted.

Although it does not specifically limit as a compound which has an acid group, as long as a side chain can be introduce|transduced into the polyolefin resin (A) which is a main chain, unsaturated carboxylic acid and its acid anhydride are mentioned preferably. Examples of unsaturated carboxylic acids and their anhydrides include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaric acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, Glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornedicarboxylic anhydride, tetrahydrophthalic anhydride, etc. These unsaturated carboxylic acids and their acid anhydrides may be used alone or in combination of two or more. Among these unsaturated carboxylic acids and their acid anhydrides, maleic anhydride is preferred because an adhesive composition having more excellent adhesive strength can be easily obtained.

As an acid-modified polyolefin resin, a commercial item can also be used. Examples of commercially available acid-modified polyolefin-based resins include ADMER (registered trademark) (manufactured by Mitsui Chemicals), UNISTOLE (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (Polyram), ororevac (registered). trademark) (manufactured by ARKEMA Corporation), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.

The compounding amount of the compound having an acid group that reacts with the polyolefin-based resin (A) as the precursor is the same as 100 parts by mass of the polyolefin-based resin (A) as the precursor, preferably 0.1 to 5 parts by mass , more preferably 0.2 to 3 parts by mass, still more preferably 0.2 to 1.0 parts by mass. When the compounding amount of the compound having the above-mentioned acid group is in the above-mentioned range, the adhesive composition system is more excellent in the adhesion strength.

(Silane-modified polyolefin-based resin) The term "silane-modified polyolefin-based resin" as used herein means that the polyolefin-based resin (A) as a precursor reacts with a compound having a silane group to form a polymer in the main chain. The olefin-based resin (A) is a polymer in which a silyl group is introduced as a side chain. As for the method and conditions for introducing the silyl group of the compound having a silyl group as the side chain of the polyolefin-based resin (A) as the main chain, a known method for introducing the side chain can be adopted.

The compound having a silyl group is not particularly limited as long as it can be introduced as a side chain in the polyolefin-based resin (A) serving as the main chain, but an unsaturated silane compound is preferably used. The unsaturated silane compound is preferably an ethylene silane compound, and examples thereof include ethylene trimethoxy silane, ethylene triethoxy silane, ethylene tripropoxy silane, ethylene triisopropoxy silane, and ethylene tributoxy silane. , Ethylene Tripentyloxy Silane, Ethylene Triphenoxy Silane, Ethylene Tribenzyloxy Silane, Ethylene Trimethylene Dioxy Silane, Ethylene Triethylene Dioxy Silane Acetyloxysilane, ethylene tricarboxysilane, etc. These unsaturated silane compounds may be used alone or in combination of two or more.

Specific examples of silane-modified polyolefin-based resins include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers. Among them, silane-modified low-density polyethylene and silane-modified ultra-low density polyethylene are preferred. Silane-modified polyethylene resins such as density polyethylene and silane-modified linear low-density polyethylene.

As a silane-modified polyolefin resin, a commercial item can also be used. Examples of commercially available silane-modified polyolefin-based resins include LINKLON (registered trademark) (manufactured by Mitsubishi Chemical Corporation). Among LINKLONs, LINKLON of low-density polyethylene systems and linear low-density polyethylene are preferred. LINKLON of polyethylene series, LINKLON of ultra-low density polyethylene series, and LINKLON of ethylene-vinyl acetate copolymer series.

The compounding amount of the compound having a silyl group to react with the polyolefin-based resin (A) as the precursor is the same as 100 parts by mass of the polyolefin-based resin (A) as the precursor, preferably 0.1 to 10 parts by mass, More preferably, it is 0.3-7 mass parts, More preferably, it is 0.5-5 mass parts. When the compounding amount of the compound having the above-mentioned silane group is in the above-mentioned range, the adhesive composition containing the obtained silane-modified polyolefin-based resin is more excellent in adhesive strength.

The weight average molecular weight (Mw) of the polyolefin-based resin (A) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 25,000 to 250,000, still more preferably 30,000 to 150,000. When the above-mentioned weight average molecular weight (Mw) is in the above-mentioned range, even when the content of the polyolefin-based resin (A) in the adhesive composition is large, the shape of the sheet formed by the adhesive composition can be easily maintained. The "weight-average molecular weight (Mw)" as used herein refers to a value obtained by standard polyethylene conversion using gel permeation chromatography using tetrahydrofuran as a solvent.

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 a non-modified polyolefin-based resin. The content of the modified polyolefin-based resin (A1) is preferably 50 to 100 mass %, more preferably 65 to 100 mass %, relative to the total amount (100 mass %) of the aforementioned polyolefin-based resin (A). More preferably, it is 80 to 100 mass %, and still more preferably, it is 90 to 100 mass %. When the content of the above-mentioned modified polyolefin-based resin (A1) is in the above-mentioned range, the adhesive composition-based adhesive strength is more excellent.

The content of the polyolefin-based resin (A) is preferably 30 to 95% by mass, more preferably 45 to 90% by mass, and still more preferably 50 to 85% by mass. The so-called "active ingredient of the adhesive composition" here refers to the component that removes the solvent contained in the adhesive composition. When the content of the polyolefin-based resin (A) is in the above range, the adhesive composition can be made more excellent in adhesive strength.

<Thermosetting component (B)> The adhesive composition of the present invention contains the thermosetting component (B). As a result, it is easy to obtain excellent bonding strength on the bonding surface between the adhesive layer of the sealing material and the object to be sealed. The term "thermosetting component (B)" as used herein refers to a component that becomes a network structure when heated and hardens into an insoluble and infusible state.

As a thermosetting component (B), a thermosetting epoxy resin, a melamine resin, a urea resin, a maleimide resin, etc. are mentioned, for example. As the aforementioned thermosetting component (B), it is preferable to contain a thermosetting epoxy resin (B1). The term "thermosetting epoxy resin (B1)" as used herein refers to an epoxy compound that forms a network structure when heated and hardens into an insoluble and infusible state. Furthermore, as the above-mentioned thermosetting epoxy resin (B1), it is preferable to contain a polyfunctional epoxy resin (B2). The term "polyfunctional epoxy resin (B2)" as used herein refers to a compound having at least two or more epoxy groups in the molecule.

As the polyfunctional epoxy resin (B2), since it becomes easier to obtain excellent adhesive strength on the bonding surface between the adhesive layer of the sealing material and the object to be sealed, it is preferable to have 2 of the 2 epoxy groups in the molecule. Functional epoxy resin. Examples of bifunctional epoxy resins include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether. ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac epoxy resin (such as phenol novolac epoxy resin, cresol novolak ring Aromatic epoxy compounds such as oxygen resin, brominated phenol novolac epoxy resin), etc.; hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S bicyclic Alicyclic epoxy compounds such as oxypropyl ether; pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalate diglycidyl ester, new Pentylene Glycol Diglycidyl Ether, Trimethylolpropane Polyglycidyl Ether, 2,2-bis(3-epoxypropyl-4-glycidoxyphenyl)propane, Dimethylol Aliphatic epoxy compounds such as tricyclodecane diglycidyl ether; etc. These bifunctional epoxy resins can be used alone or in combination of two or more.

The content of the thermosetting component (B) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30 mass %. The so-called "active ingredient of the adhesive composition" here refers to the component that removes the solvent contained in the adhesive composition. When the content of the above-mentioned thermosetting component (B) is in the above-mentioned range, it becomes easy to maintain excellent adhesiveness on the bonding surface of the adhesive layer of the sealing material and the object to be sealed.

The content of the thermosetting component (B) in the adhesive composition is preferably 5 to 110 parts by mass, more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the polyolefin-based resin (A). When the content of the thermosetting component (B) is within this range, the adhesive layer formed from the adhesive composition is more excellent in water vapor barrier properties.

<Curing catalyst (C)> The adhesive composition of the present invention preferably further contains a curing catalyst (C) from the viewpoint of making it easier to obtain an adhesive layer with higher adhesive strength. The term "hardening catalyst (C)" here refers to a catalyst that hardens the thermosetting component (B).

As the curing catalyst (C), an imidazole-based curing catalyst is preferred from the viewpoint of being suitable for curing the thermosetting component (B). Examples of the imidazole-based hardening catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2- -Phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. These imidazole-based hardening catalysts can be used alone or in combination of two or more. Among these imidazole-based hardening catalysts, 2-ethyl-4-methylimidazole is preferred.

The content of the curing catalyst (C) contained in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the thermosetting component (B). Since the content of the above-mentioned hardening catalyst (C) is in the above-mentioned range, the adhesive layer has excellent adhesion even at high temperature.

<Silane coupling agent (D)> The adhesive composition of the present invention may further contain a silane coupling agent (D). As a result, the bonding strength under normal temperature and high temperature environments becomes more excellent. The term "silane coupling agent (D)" as used herein refers to an organosilicon compound having two or more different reactive groups in the molecule.

The silane coupling agent (D) is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule from the viewpoint of obtaining excellent bonding strength. Examples of such silane coupling agents include polymerizable unsaturated group-containing silicon compounds such as ethylenetrimethoxysilane, ethylenetriethoxysilane, and methacryloyloxypropyltrimethoxysilane; 3-ring Oxypropoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxy Silicon compounds with epoxy structure such as octyl trimethoxysilane; 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, Amino-containing silicon compounds such as N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3-isocyanatopropyltriethyl Oxysilane; etc. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent (D) contained in the adhesive composition is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 1.0 parts by mass, relative to 100 parts by mass of the polyolefin-based resin (A). When the content of the silane coupling agent (D) is in the above range, even when exposed to a high-temperature and high-humidity environment for a long time, it becomes easy to maintain excellent adhesion on the bonding surface between the adhesive layer of the sealing material and the object to be sealed. the continuity.

(Solvent) When the adhesive composition is in the form of a solution by adding a solvent, and the adhesive layer is formed by coating, it is preferable from the viewpoint that it is easy to adjust the adhesive composition to a property suitable for coating. Examples of the solvent include aromatic hydrocarbon-based solvents such as benzene and toluene; ester-based solvents such as ethyl acetate and butyl acetate; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon-based solvents such as n-pentane, n-hexane, n-heptane, etc.; alicyclic hydrocarbon-based solvents such as cyclopentane, cyclohexane, methylcyclohexane, etc.; and the like. Among these, ketone-based solvents are preferred, and among them, dimethyl ethyl ketone is preferred.

The amount of the solvent used in the preparation of the adhesive composition is used so that the solid content concentration is preferably 8 to 48 mass %, more preferably 8 to 38 mass %, and still more preferably 8 to 28 mass %. Can.

(Other components) In addition to the aforementioned polyolefin-based resin (A), the aforementioned thermosetting component (B), the aforementioned curing catalyst (C), the aforementioned silane coupling agent (D), and the aforementioned solvent, the adhesive composition is In addition, other components may be further contained within a range that does not impair the curing of the present invention. Examples of other components include ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, and adhesion imparting agents.

[Base layer] By having the base layer, the gas barrier film of the present invention can effectively peel off the release sheet while suppressing damage or deterioration of the gas barrier layer. The base layer is preferably directly laminated on the release sheet. In addition, the base layer is interposed between the release sheet and the gas barrier layer.

The thickness of the base layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. When the thickness of the above-mentioned base layer is in the above-mentioned range, damage or deterioration of the gas barrier layer can be easily suppressed, and the release sheet can be easily and efficiently peeled off and removed. When the base layer is as thin as about 0.1 to 10 μm, the thickness of the entire gas barrier film can be easily adjusted to a smaller range, which is suitable for applications that require miniaturization in electronic devices such as organic EL elements. When the gas-barrier film is composed of a base material and a gas-barrier layer, when the base material has such a thin thickness, handling of the gas-barrier film may be difficult. In the present invention, since the release sheet exists on the side opposite to the side where the gas barrier layer of the base layer is laminated, the problem of workability is eliminated. Furthermore, since the release sheet is usually removed after applying the gas barrier film to the object to be sealed, the member derived from the gas barrier film remaining in the sealing body can be made thinner. When the base layer is made thinner, the thickness of the base layer may be preferably 1 to 20 μm depending on the application, and in this case, the thickness of the base layer is more preferably 3 to 15 μm.

The maximum cross-sectional height (Rt) of the roughness curve of the base layer on the side of the base layer in contact with the release sheet of the base layer, or the base layer on the opposite side of the base layer in contact with the release sheet of the base layer, is preferably 1 to 300 nm. , more preferably 1 to 200 nm, still more preferably 2 to 150 nm. The maximum cross-sectional height (Rt) of the base layer can be measured by observing the surface of the base layer using an optical interference microscope. For example, in the production step of the gas barrier film, when the base layer is formed on the release sheet, the surface of the exposed base layer can be used as the measurement object. When the above-mentioned maximum cross-sectional height (Rt) is within the above-mentioned range, the gas barrier layer can be appropriately protected, and the release sheet can be easily peeled off and removed efficiently. In addition, the above-mentioned maximum cross-sectional height (Rt) can be adjusted to the above-mentioned range by adjusting the average particle size or content of the inorganic filler described later.

(Composition for base layer) The base layer of the present invention is preferably formed from a composition for base layer containing an energy ray curable component. Moreover, it is also preferable that the composition for base layers contains a thermoplastic resin. As a result, damage or deterioration of the gas barrier layer can be easily suppressed, and the release sheet can be easily peeled off and removed efficiently. Hereinafter, each component contained in the composition for the base layer suitable as a material for forming the base layer will be described.

<Thermoplastic resin> By containing a thermoplastic resin in the base layer composition, it becomes easy to obtain a base layer having moderate flexibility. The term "thermoplastic resin" as used herein refers to a resin that is melted or softened by heating, and has the property of solidifying when cooled.

As the thermoplastic resin, for example, resins having an aromatic ring structure and resins having a ring structure such as an alicyclic structure can be cited, but resins having an aromatic ring structure are preferred. As resins having an aromatic ring structure, for example, polysilicon-based resins, polyarylate-based resins, polycarbonate-based resins, and alicyclic hydrocarbon-based resins are preferable, and among them, polysilicon-based resins are preferable. Furthermore, the polysiloxane-based resin may be a modified polysiloxane-based resin. The term "polysilicon-based resin" as used herein refers to a resin composed of a polymer compound having a siloxane group (-SO ₂ -) in the main chain. As a polysilicon resin, the resin which consists of the polymer compound which has the repeating unit represented by following (a)-(h) is mentioned. Among these, polyether resin and polysilicon are preferable as polysilicon resins, and among them, polysiloxane is more preferable.

The glass transition temperature (Tg) of the thermoplastic resin is preferably 140°C or higher, more preferably 160°C or higher, and even more preferably 180°C or higher. Here, the "glass transition temperature (Tg)" refers to the tanδ (loss of elasticity) obtained by viscoelasticity measurement (measured in a tensile mode at a frequency of 11 Hz, a temperature increase rate of 3°C/min in the range of 0 to 250°C) The temperature at the maximum point of the rate/storage elastic rate). When the above-mentioned glass transition temperature (Tg) is in the above-mentioned range, it becomes easy to form a base layer with excellent heat resistance.

The weight average molecular weight (Mw) of the thermoplastic resin is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, and more preferably 500,000 to 2,000,000. In addition, the molecular weight distribution (Mw/Mn) of the thermoplastic resin is preferably 1.0 to 5.0, more preferably 2.0 to 4.5. The so-called "weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)" here refer to the polystyrene conversion values measured by gel permeation chromatography (GPC).

The content of the thermoplastic resin is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass relative to the total amount (100% by mass) of the active ingredients of the aforementioned composition for base layer. quality%. In addition, the term "active ingredient of the composition for base layer" here refers to the component that removes the solvent contained in the composition for base layer. When the content of the thermoplastic resin is in the above range, it becomes easy to obtain a gas barrier film having moderate flexibility and strength.

(Energy ray curable component) By forming the base layer from the composition for base layer containing the energy ray curable component, in particular, a gas barrier with high transparency, low birefringence and high optical isotropy can be obtained Advantages of Sex Films. When a gas barrier film is obtained, when a general polyester base material is used, the optical anisotropy is high, and the light extraction property is deteriorated when it is applied to a display or the like. Moreover, although there exists a base material with high optical isotropy, such as a cycloolefin polymer, it is difficult to handle and it is difficult to improve the manufacturing suitability in some cases. By forming the base layer from the composition for the base layer containing the energy ray curable component, a gas barrier film with high optical isotropy can be easily obtained. In addition, the composition for a base layer has the advantage of being easy to obtain a base layer excellent in solvent resistance by containing an energy ray curable component.

The so-called energy ray-curable component refers to a resin that is transformed into a cured product by irradiating energy rays such as electron beams, ultraviolet rays, etc., or heating, to initiate a curing reaction. The energy ray curable component is usually a mixture containing a polymerizable compound as a main component. Also, the polymerizable compound refers to a compound having an energy ray polymerizable functional group. As the energy ray polymerizable functional group, ethylenically unsaturated groups such as (meth)acryloyl group, vinyl group, allyl group, and styryl group are exemplified.

Examples of the polymerizable compound include (meth)acrylate derivatives, and specific examples of the (meth)acrylate derivatives include tricyclodecane dimethanol di(meth)acrylate, polyethylene glycol Alcohol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 1,10-decanedi Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]perylene, etc. .

The molecular weight of the (meth)acrylate derivative is usually 3000 or less, preferably 200 to 2000, and more preferably 200 to 1000.

The energy ray curable component may contain an oligomer as a polymerizable compound. Examples of the oligomer include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyol acrylate oligomers, and the like. In addition, the energy ray curable component may contain a polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator.

As an energy-beam curable component, the component (ultraviolet-curable component) which hardens|cures by ultraviolet irradiation is preferable. By using the ultraviolet curable component, the layer composed of the cured product of the energy ray curable component can be efficiently formed.

As the polymerization initiator, a photopolymerization initiator is preferable, and specifically, an alkylphenone-based photopolymerization initiator, a phosphorus-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, Benzophenone-based photopolymerization initiators and thioxanthone-based photopolymerization initiators, among which, phosphorus-based photopolymerization initiators are more preferred.

Examples of the phosphorus-based photopolymerization initiator include 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)- Phenylphosphine oxide, ethyl(2,4,6-trimethylbenzyl)-phenylphosphinate, bis(2,6-dimethoxybenzyl)-2,4 , 4-trimethyl-pentyl phosphine oxide, etc.

The content of the polymerization initiator contained in the energy ray curable component is preferably 0.5 to 6.5 parts by mass, more preferably 0.5 to 5.5 parts by mass, and still more preferably 0.5 to 0.5 parts by mass relative to 100 parts by mass of the aforementioned polymerizable compound. 4.5 parts by mass.

The content of the energy ray curable component is preferably 30 to 90% by mass, more preferably 50 to 70% by mass, relative to the total amount (100% by mass) of the active ingredients in the above-mentioned composition for base layers. In addition, the term "active ingredient of the composition for base layer" here refers to the component that removes the solvent contained in the composition for base layer. When the content of the above-mentioned energy ray curable component is in the above-mentioned range, it becomes easy to obtain a base layer excellent in solvent resistance.

<Inorganic filler> The base layer composition may contain an inorganic filler. Examples of inorganic substances constituting the inorganic filler include metal oxides such as silicon dioxide, aluminum oxide, zirconium oxide, titanium dioxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Metal fluorides such as magnesium fluoride, sodium fluoride, etc.; etc. Inorganic fillers may have their surfaces modified with organic compounds.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 to 100 nm. When the average particle diameter of the inorganic filler is too small, it may be difficult to sufficiently improve the releasability of the release film. On the other hand, if the average particle diameter of the inorganic filler is in such a small range, it is easy to maintain the gas barrier properties of the gas barrier layer formed on the base layer at a high level. The average particle size of the inorganic filler can be measured by dynamic light scattering using a particle size distribution analyzer.

The content of the inorganic filler is preferably 10 to 70 mass %, more preferably 50 to 70 mass %, with respect to the total amount (100 mass %) of the active ingredient in the above-mentioned base layer composition. In addition, the term "active ingredient of the composition for base layer" here refers to the component that removes the solvent contained in the composition for base layer. When the content of the above-mentioned inorganic filler is in the above-mentioned range, the release sheet can be easily peeled off and removed efficiently while protecting the gas barrier layer appropriately.

When the composition for a base layer used in one aspect of the present invention contains a thermoplastic resin, the energy ray curable component contains a polymerizable compound and a polymerization initiator, and the composition for a base layer does not contain an inorganic filler, the thermoplastic resin, the polymerizable compound and the The total content of the polymerization initiators is preferably 70 to 100 mass %, more preferably 80 to 100 mass %, and even more preferably 90 mass %, relative to the total amount (mass %) of the active ingredients of the aforementioned base layer composition. ~100 mass %. In addition, the term "active ingredient of the composition for base layer" here refers to the component that removes the solvent contained in the composition for base layer.

(Solvent) The composition for the base layer is preferably in the form of a solution by adding a solvent, and in the step of forming the base layer by coating, from the viewpoint of being easy to adjust the composition for the base layer to a property suitable for coating. Examples of the solvent include aliphatic hydrocarbon-based solvents such as n-hexane and n-heptane; aromatic hydrocarbon-based solvents such as toluene and xylene; methylene chloride, vinyl chloride, chloroform, carbon tetrachloride, Halogenated hydrocarbon solvents such as 1,2-dichloroethane and monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, 2 -ketone-based solvents such as pentanone, isophorone, cyclohexanone, etc.; ester-based solvents such as ethyl acetate and butyl acetate; cellosolve-based solvents such as ethyl cellosolve; 1,3-dioxane ether solvents such as alkanes; etc. Among these, halogenated hydrocarbon-based solvents are preferred, and among them, methylene chloride is preferred.

The usage-amount of the solvent used for the preparation of the base layer composition is preferably 5 to 45 mass %, more preferably 5 to 35 mass %, and even more preferably 5 to 25 mass %, based on the solid content concentration of the thermoplastic resin. % can be used.

(Other Components) In addition to the thermoplastic resin, the energy ray curable component, the inorganic filler, and the solvent, the composition for the base layer may further contain other components within a range that does not impair the effects of the present invention. As other components, a plasticizer, antioxidant, ultraviolet absorber, etc. are mentioned, for example.

[Release Sheet] As the release sheet (first release sheet) laminated on the base layer, a conventionally known one can be used. As the release film, a conventionally known one can be used. For example, on the base material for peeling sheets, what has a peeling layer which is peeled with a peeling agent is mentioned. Examples of the base material for the release sheet include paper base materials such as transparent paper, coated paper, and high-quality paper; laminate paper laminated with thermoplastic resins such as polyethylene on these paper base materials; polyethylene terephthalic acid Plastic films of ethylene glycol resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc.; etc. Examples of the release agent include rubber-based elastomers such as polysiloxane-based resins, olefin-based resins, isoprene-based resins, butadiene-based resins, etc., long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins. resin, etc. In addition, the paper base material or the plastic film listed as the base material for the release sheet can be used as it is without providing the release layer.

When the second release sheet is used, the same or different ones may be used for the two release films of the first release sheet and the second release sheet, respectively. When using two mutually different peeling films, it is preferable to use those which have different peeling force respectively. Since the peeling force of the two peeling films is different, it is difficult to cause problems when using the gas barrier film. That is, by making the peeling force of two peeling films different, the step of peeling off the peeling film first from the gas barrier film can be performed more efficiently. The second release sheet preferably has a release layer from the viewpoint of improving the releasability with the adhesive layer. The thickness of the release sheet is preferably 10 to 300 μm, more preferably 20 to 125 μm, and even more preferably 30 to 100 μm.

[Gas-barrier layer] The gas-barrier film of the present invention can exhibit excellent gas-barrier properties with a high effect of preventing the permeation of gases such as oxygen or water vapor by having a gas-barrier layer. In addition, the gas barrier layer is interposed between the base layer and the adhesive layer.

Even if the gas barrier layer is one layer, the gas barrier properties satisfying a certain level can be obtained, but by laminating two or more gas barrier layers, the effect of improving the gas barrier properties can be obtained. The two or more gas barrier layers can be of the same thickness or of different thicknesses. The thickness of the gas barrier layer 1 is usually in the range of 20 nm to 50 μm, preferably 30 nm to 1 μm, and more preferably 40 nm to 500 nm. When the thickness of the first gas barrier layer is within the above range, it becomes easy to obtain a gas barrier film having a gas barrier property satisfying a certain level, which is highly effective in preventing the permeation of gases such as oxygen and water vapor. In the case of two or more gas barrier layers, each gas barrier layer is preferably a layer formed of the same composition. Thereby, the interlayer adhesion between two or more gas barrier layers can be improved.

A preferable aspect of the gas barrier layer is selected from (i) a gas barrier layer composed of an inorganic vapor deposition film, (ii) a gas barrier layer comprising a gas barrier resin, and (iii) a modified gas barrier layer comprising a polymer compound A gas barrier layer formed on the surface of the layer (hereinafter, also referred to as "polymer layer") [in this case, the so-called gas barrier layer does not mean only the modified region, but also means "including modified At least one of the group consisting of the polymer layer of the region"]. Among them, as a more preferable aspect of the gas barrier layer, it is selected from (i) a gas barrier layer composed of an inorganic vapor-deposited film and (iii) a gas barrier layer composed of a modified polymer layer surface At least 1 species in the group.

(i) Gas-barrier layer composed of an inorganic vapor-deposited film As the inorganic vapor-deposited film, a vapor-deposited film of an inorganic compound or a metal is exemplified. Examples of the raw material of the vapor-deposited film of inorganic compounds include inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, zinc tin oxide, etc.; silicon nitride, aluminum nitride, titanium nitride, etc. Inorganic nitrides; Inorganic carbides; Inorganic sulfides; Inorganic oxide nitrides such as silicon oxide nitride; Inorganic oxide carbides; Inorganic nitride carbides; As the raw material of the metal vapor-deposited film, aluminum, magnesium, zinc, and tin can be cited. The raw materials of these inorganic compounds and metal vapor-deposited films can be used alone or in combination of two or more.

The inorganic vapor-deposited film is preferably an inorganic vapor-deposited film using as a raw material at least one selected from the group consisting of inorganic oxides, inorganic nitrides, and metals, from the viewpoint of gas barrier properties. Among these inorganic vapor-deposited films, from the viewpoint of transparency, an inorganic vapor-deposited film using at least one kind selected from the group consisting of inorganic oxides and inorganic nitrides as a raw material is more preferable. In addition, the inorganic vapor-deposited film may be a single layer or a multilayer.

From the viewpoints of gas barrier properties and handleability, the thickness of the inorganic vapor deposition film is preferably 1 to 2,000 nm, more preferably 3 to 1,000 nm, still more preferably 5 to 500 nm, and still more preferably 40 to 200 nm.

The method of forming the inorganic vapor deposition film is not particularly limited, and a well-known method is used. Examples of methods for forming the inorganic vapor deposition film include PVD methods such as vacuum deposition, sputtering, and ion plating; CVD methods such as thermal CVD, plasma CVD, and optical CVD; atomic layer deposition ( ALD method); etc.

(ii) Gas Barrier Layer Containing Gas Barrier Resin Examples of the gas barrier resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene Resins that are hard to permeate gases such as oxygen or water vapor, such as vinylidene chloride and polychlorotrifluoroethylene.

From the viewpoint of gas barrier properties, the thickness of the gas barrier layer including the gas barrier resin is preferably 1 to 2,000 nm, more preferably 3 to 1,000 nm, still more preferably 5 to 500 nm, and still more preferably 40～200nm.

As a method of forming the gas-barrier layer containing a gas-barrier resin, for example, a solution containing a gas-barrier resin is applied to a release film or a substrate, and the obtained coating film is appropriately dried. The coating method of the solution containing the gas barrier resin is not particularly limited, and examples include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating. well-known coating methods such as method. As the drying method of the coating film, well-known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be exemplified.

(iii) Gas-barrier layer formed by modifying the surface of the polymer layer As the polymer compound used in the gas-barrier layer formed by modifying the surface of the polymer layer, silicon-containing polymer compounds, polyamides Amine, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polyamide, polyether sulfide, polyphenylene vulcanizate Compounds, polyarylates, acrylic resins, alicyclic hydrocarbon resins, aromatic polymers, etc. These polymer compounds may be used alone or in combination of two or more.

In addition to the above-mentioned polymer compound, the polymer layer may further contain other components within a range that does not impair the effects of the present invention. As other components, a hardener, an antiaging agent, a light stabilizer, a flame retardant, etc. are mentioned, for example. The content of the polymer compound is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total amount (100% by mass) of the active ingredients in the composition for the polymer layer. Furthermore, the term "active ingredient of the polymer layer composition" here refers to a component that removes the solvent contained in the polymer layer composition. When the content of the above-mentioned polymer compound is in the above-mentioned range, a gas-barrier layer with excellent gas-barrier properties can be easily formed.

The thickness of the polymer layer is not particularly limited, but is preferably 20 nm to 50 μm, more preferably 30 nm to 1 μm, and even more preferably 40 nm to 500 nm.

The polymer layer can be formed by, for example, dissolving or dispersing a polymer compound in a solution of an organic solvent, coating the release film or the base material layer by a known coating method, and drying the obtained coating film.

Examples of the organic solvent include aromatic hydrocarbon-based solvents such as benzene and toluene; ester-based solvents such as ethyl acetate and butyl acetate; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon-based solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon-based solvents such as cyclopentane and cyclohexane; and the like. These organic solvents may be used alone or in combination of two or more.

The coating method of dissolving or dispersing the polymer compound in the organic solvent is not particularly limited, and examples include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, and air knife coating. Coating method, roll knife coating method, die coating method, screen printing method, spraying method, gravure offset printing method, etc.

As a drying method for forming the coating film of the polymer layer, well-known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be exemplified. The heating temperature is preferably 80 to 150°C, and the heating time is usually several tens of seconds to several tens of minutes.

As the gas barrier layer formed on the surface of the modified polymer layer, the method of modifying the surface of the polymer layer includes ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like. The ion implantation treatment is a method of implanting accelerated ions into the polymer layer and modifying the polymer layer, as will be described later. Plasma treatment is a method of modifying the polymer layer by exposing the polymer layer to the plasma. For example, the plasma treatment can be performed according to the method described in Japanese Patent Laid-Open No. 2012-106421. Ultraviolet irradiation treatment is a method of modifying the polymer layer by irradiating ultraviolet rays on the polymer layer. For example, the ultraviolet modification treatment is performed according to the method described in Japanese Patent Application Laid-Open No. 2013-226757.

The gas barrier layer formed by modifying the surface of the polymer layer is preferably obtained by performing ion implantation on a layer containing a polymer compound containing silicon, since the gas barrier properties are more excellent. Examples of the polymer compound containing silicon include polysilazane-based compounds, polycarbosilane-based compounds, polysilane-based compounds, polyorganosiloxane-based compounds, poly(disilylene phenylene)-based compounds, and A poly(disilylene ethynylene)-based compound and the like, among these, a polysilazane-based compound is preferred.

The polysilazane-based compound is a compound having a repeating unit including a -Si-N- bond (silazane bond) in the molecule. Specifically, a compound having a repeating unit represented by the following general formula (1) is preferred.

In the general formula (1), n represents a repeating unit and represents an integer of 1 or more. Also, Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, and an unsubstituted or substituted group non-hydrolyzable groups such as aryl groups or alkylsilyl groups.

Examples of the alkyl group having an unsubstituted or substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. , n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and other alkyl groups having 1 to 10 carbon atoms. Examples of the cycloalkyl group having an unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Examples of the alkenyl group having an unsubstituted or substituted alkenyl group include carbons such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl. Alkenyl of 2 to 10.

As the substituent when the aforementioned alkyl group, the aforementioned cycloalkyl group and the aforementioned alkenyl group have a substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxyl group; thiol group; epoxy group can be mentioned. glycidoxy; (meth)acryloyloxy; unsubstituted or substituted aryl groups such as phenyl, 4-methylphenyl, 4-chlorophenyl, etc.; and the like. Furthermore, in this specification, the description of "(meth)acryloyl" means "acryloyl" and/or "methacryloyl". Similarly, the description of "(meth)acryloyl group" also means "acryloyl group" and/or "methacryloyl group".

Examples of the aryl group having an unsubstituted or substituted aryl group include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Examples of the substituent when the aforementioned aryl group has a substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; and methoxy groups. , alkoxy with 1 to 6 carbon atoms such as ethoxy; nitro; cyano; hydroxyl; thiol; epoxy; glycidoxy; (meth)acryloyloxy; phenyl, Unsubstituted or substituted aryl groups such as 4-methylphenyl, 4-chlorophenyl, etc.; and the like.

Examples of the alkylsilyl group include trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, methyldiethylsilyl, dimethylsilyl, Diethylsilyl, methylsilyl, ethylsilyl, etc.

Among these, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and among them, a hydrogen atom is more preferable. The polysilazane-based compound having the repeating unit represented by the general formula (1) may be an inorganic polysilazane in which all of Rx, Ry, and Rz are hydrogen atoms, and at least one of Rx, Ry, and Rz is not a hydrogen atom. Any of organopolysilazane.

In addition, in the present invention, a modified polysilazane can also be used as the polysilazane-based compound. Examples of the modified polysilazane include JP 62-195024 A, JP 2-84437 A, JP 63-81122 A, JP 1-138108 A, and the like. , Japanese Patent Laid-Open No. 2-175726, Japanese Patent Laid-Open No. 5-238827, Japanese Patent Laid-Open No. 5-238827, Japanese Patent Laid-Open No. 6-122852, Japanese Patent Laid-Open No. 6-306329, Japanese Patent Laid-Open No. 6-306329 - Those described in Japanese Patent Laid-Open No. 299118, Japanese Patent Laid-Open No. 9-31333, Japanese Patent Laid-Open No. 5-345826, Japanese Patent Laid-Open No. 4-63833, and the like. Among these, as the polysilazane-based compound, from the viewpoints of easy availability and formation of an ion-implanted layer having excellent gas barrier properties, it is preferable that all of Rx, Ry, and Rz are in the general formula (1). It is a perhydropolysilazane of hydrogen atoms. In addition, as the above-mentioned polysilazane-based compound, commercially available products such as glass coating materials can also be used as they are. The aforementioned polysilazane-based compounds may be used alone or in combination of two or more.

Moreover, although the number average molecular weight (Mn) of the said polysilazane type compound is not specifically limited, The compound of 100-50,000 can be used suitably. When the number-average molecular weight (Mn) can be obtained by gel permeation chromatography, it is obtained as a standard polystyrene conversion value.

Examples of ions implanted into the polymer layer include ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, and the like; methane, Ions of alkane-based gases such as ethane; ions of olefin-based gases such as ethylene and propylene; ions of diene-based gases such as pentadiene and butadiene; ions of acetylene-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 cycloolefin-based gases such as cyclopentene; ions of metals; ions of organosilicon compounds; Wait. These ions can be used alone or in combination of two or more. Among them, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be implanted more easily and a gas barrier layer with better gas barrier properties can be formed.

As a method of implanting ions, a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions into plasma, and the like can be mentioned. Among these methods, the latter method of implanting plasma ions (plasma ion implantation) is preferable because the desired gas barrier layer can be easily formed.

In the plasma ion implantation method, for example, a plasma can be generated in an environment containing a plasma generating gas such as a rare gas, and a negative high voltage pulse can be applied to the polymer layer to implant ions (cations) in the plasma. This is performed on the surface portion of the polymer layer. More specifically, the plasma ion implantation method can be implemented by the method described in WO2010/107018 pamphlet and the like.

The implantation amount of ions can be appropriately determined according to the purpose of use of the gas barrier film (necessary gas barrier properties, transparency, etc.). By ion implantation, the thickness of the region into which ions are implanted can be regulated by the type of ions or the implantation conditions such as applied voltage and processing time. Although it can be adjusted according to the thickness of the polymer layer or the purpose of use of the gas barrier film, Preferably it is 10-400 nm.

The implanted ions can be confirmed by performing elemental analysis measurement in the vicinity of 10 nm from the surface of the polysilazane layer using X-ray photoelectron spectroscopy (XPS).

The gas barrier layer may be a single layer, or may also be a multiple layer. For example, (i) a gas barrier layer composed of an inorganic vapor deposition film and (iii) a gas barrier layer formed by modifying the surface of the polymer layer can be used in combination. When the aforementioned adhesive layer is laminated on the gas barrier layer through the adhesion enhancing layer, the layer adjacent to the adhesion enhancing layer is preferably a gas barrier layer composed of an inorganic vapor-deposited film.

[Adhesion-enhancing layer] If the gas barrier film of the present invention is formed by laminating a base layer, a gas barrier layer and an adhesive layer in this order, it is not particularly limited, but the adhesive layer can pass through the adhesive layer. The reinforcement layer is laminated on the gas barrier layer. The gas-barrier film of the present invention can improve the adhesion between the gas-barrier layer and the adhesive layer by having an adhesion-enhancing layer.

The thickness of the adhesion enhancing layer is preferably 700 nm or less, more preferably 50 to 700 nm, still more preferably 100 to 500 nm, still more preferably 150 to 400 nm. When the thickness of the adhesion enhancing layer is in the above-mentioned range, the effect of improving the adhesion between the gas barrier layer and the adhesive layer can be appropriately exhibited.

The adhesion enhancing layer is preferably a layer containing an organic substance. Specifically, a layer containing a polyester resin; a layer containing an acryl-based resin; a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, and the like include a curable composition containing an energy ray curable compound. A layer composed of a cured product of a thermosetting resin; a layer composed of a cured product of a curable composition containing a thermosetting resin, such as thermosetting epoxy resin, melamine resin, etc.; etc. The adhesion-enhancing layer is preferably a layer composed of a cured product of a curable composition containing a thermosetting epoxy resin. By using a curable composition containing a thermosetting epoxy resin, an excellent adhesive can be formed due to the adhesion between the gas barrier layer and the adhesive layer, especially the adhesion after storage under high temperature and high humidity conditions. Adhesion Enhancement Layer.

A thermosetting epoxy resin is a compound (henceforth, also called a "polyfunctional epoxy compound") which has at least 2 or more epoxy groups in a molecule|numerator. As the thermosetting epoxy resin that can be used in the adhesion enhancing layer, epoxy resins having a glycidylamine group derived from m-xylylenediamine diamine, epoxy resins having a glycidylamine group derived from 1,3-bis( Epoxy resins with glycidylamine groups derived from aminomethyl)cyclohexane, epoxy resins with glycidylamine groups derived from diaminodiphenylmethane, epoxy resins with glycidylamine groups derived from p-aminophenol Epoxy resins with glycidylamine groups or glycidoxy groups, epoxy resins with glycidoxy groups derived from bisphenol A, epoxy resins with glycidoxy groups derived from bisphenol F , epoxy resins with glycidoxy groups derived from novolac, epoxy resins with glycidoxy groups derived from resorcinol, and the like. Among these thermosetting epoxy resins, an epoxy resin containing an aromatic ring in the molecule is preferable. These thermosetting epoxy resins can be used alone or in combination of two or more.

The content of the thermosetting epoxy resin in the curable composition is preferably 10 to 60 mass %, more preferably 20 to 50 mass %, relative to the total solid content of the curable composition. Furthermore, the term "solid content of the curable composition" here refers to the component that removes the solvent contained in the curable composition.

The curable composition preferably contains a polyfunctional amine compound. In the curable composition containing the polyfunctional amine compound, since the curing reaction proceeds more efficiently, the adhesion-enhancing layer can be efficiently formed. Examples of the polyfunctional amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, p-xylylenediamine, 1,3-bis(aminomethyl) group) cyclohexane, diaminodiphenylmethane, m-phenylenediamine, etc. These polyfunctional amine compounds can be used alone or in combination of two or more. The content of the polyfunctional amine compound in the curable composition is preferably 25 to 80% by mass, more preferably 35 to 75% by mass, relative to the total solid content of the curable composition.

The curable composition may contain a silane coupling agent. When the curable composition contains a silane coupling agent, an excellent adhesion-enhancing layer can be formed due to the adhesion with the gas barrier layer.

As the silane coupling agent, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -(2-Aminoethyl)aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-(2-aminoethyl) ) Amine silane coupling agents such as aminopropylmethyldiethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Epoxysilane coupling agent such as; 3-mercaptopropyltrimethoxysilane; 3-methacryloyloxypropyltrimethoxysilane; Japanese Patent Laid-Open No. 2000-239447, Japanese Patent Laid-Open No. 2001-40037 etc. The polymer silane coupling agent described in; etc. These silane coupling agents may be used alone or in combination of two or more.

When the curable composition contains a silane coupling agent, the content of the silane coupling agent is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the thermosetting epoxy resin.

The curable composition may contain a solvent. Examples of the solvent include aliphatic hydrocarbon-based solvents such as n-hexane and n-heptane; aromatic hydrocarbon-based solvents such as toluene and xylene; methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, 1 , Halogenated hydrocarbon solvents such as 2-dichloroethane and monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, 2- Ketone-based solvents such as pentanone, isophorone, and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; cellosolve-based solvents such as ethyl cellosolve; 1,3-dioxane etc. ether-based solvents; etc. These solvents can be used alone or in combination of two or more.

The content of the solvent in the curable composition is not particularly limited, but is preferably 85 to 99 mass %, more preferably 90 to 97 mass % with respect to the total amount of the curable composition.

The curable composition may contain various additives within a range that does not inhibit the effects of the present invention. As this additive, an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, a coloring pigment, etc. are mentioned. The content of these additives can be appropriately adjusted according to the purpose.

The curable composition can be prepared by appropriately mixing and stirring the aforementioned thermosetting epoxy resin and, if necessary, other components according to a conventional method.

The adhesion-enhancing layer can be formed by, for example, applying a resin composition for forming an adhesion-enhancing layer, such as a curable composition, on the gas barrier layer, and curing or drying the resulting coating film according to a conventional method. As the coating method, a normal wet coating method can be used. For example, bar coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, gravure offset printing method, spin coating method, blade coating method, etc.

When hardening or drying the coating film, it is sufficient to heat the coating film according to the usual method. The heating temperature is preferably 70 to 180°C, more preferably 80 to 150°C. The heating time is preferably 30 seconds to 10 minutes, more preferably 1 to 7 minutes.

The polyolefin-based resin (A) contained in the adhesive layer is a modified polyolefin-based resin (A1), and the gas barrier layer contains a polysilazane-based compound. In the case of a layer formed by a modification treatment, the adhesive layer is relatively Preferably, it is directly laminated on the gas barrier layer. In the above-mentioned gas barrier layer, although the adhesive layer containing the polyolefin-based resin (A) tends to be difficult to achieve adhesion, when the polyolefin-based resin (A) contains the modified polyolefin-based resin (A1), Since good adhesion is exhibited even with respect to the gas barrier layer as described above, it is possible to omit the adhesion-enhancing layer.

[Sealed body] The sealing system of the present invention uses the gas-barrier film of the present invention as a sealing material and seals the object to be sealed, and there is a problem that defects due to interlayer peeling, etc., and/or infiltration of water vapor, etc. are unlikely to occur. By. Therefore, from a long-term perspective, the sealing body is suitable for use in applications requiring the maintenance of the performance of the sealing object. That is, excellent adhesiveness is maintained on the bonding surface between the adhesive layer of the sealing material and the object to be sealed, and the original performance of the object to be sealed can be properly maintained. As the object to be sealed, at least one selected from the group consisting of organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL display elements, electronic paper elements, liquid crystal display elements, and solar cell elements can be used.

(Manufacturing method of sealing body) Although the manufacturing method of the sealing body of the present invention is not particularly limited, it preferably includes a step of attaching an adhesive layer having a gas-barrier film to a to-be-sealed body, and a step of adhering the adhesive layer having a gas barrier film to the object to be sealed. The step of peeling off the gas film. For example, when the gas barrier film of the present invention as a sealing material is in the form shown below, the second release sheet is first peeled off and removed. Next, the surface of the exposed adhesive layer and the surface of the object to be sealed are overlapped, pressurized if necessary, and heated under a desired heating condition to obtain a gas barrier that hardens the adhesive layer and the object to be sealed as a sealing material The sealing body formed by the sealing of the film. ‧First release sheet/base layer/gas barrier layer/adhesive layer/second release sheet In general, the first release sheet is the one on which the adhesive layer is formed and the object to be sealed, and then removed by peeling. The peeling removal of the first peeling sheet may be performed before or after the step of heating the gas barrier film. According to the production method of such a sealed body, even if the gas barrier film does not have a base material, the first release sheet functions as a support of the gas barrier film until the first release sheet is peeled off and removed, thereby preventing the gas barrier properties. The film is broken or deformed, and the handleability is excellent. [Example]

The following examples are given to illustrate the present invention in more detail. However, the present invention is not limited to the following examples. However, the "parts" and "%" described below are "quality standards" unless otherwise specified.

(Example 1) [Preparation of Gas Barrier Film] (1) Step of Forming Base Layer As thermoplastic resin, particles of polysiloxane resin (PSF) ("ULTRASON S3010" manufactured by BASF Corporation, Tg=180°C) were used as the thermoplastic resin. ) 60 parts were dissolved in dichloromethane to prepare a 15% solution of PSF. To this solution, 40 parts of tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ADCP) were added as an energy ray curable component and bis(2,4,6-trimethylbenzyl)-benzene One part of phosphine oxide (manufactured by BASF, "Irgacure 819") was mixed as a polymerization initiator to prepare a composition for an underlayer.

As the first release sheet, the base layer prepared above was placed on the non-treated surface of an easily adhesively treatable polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., "PET50A-4100", thickness 50 μm). The composition is applied by a die coating method to form a coating film. The coating film was dried by heating the coating film at 50° C. for 2 minutes, followed by heating at 140° C. for 2 minutes. Next, on this dry coating film, as a step sheet, the non-treated surface of an easily adhesive treated polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., "PET50A-4100", thickness 50 μm) was attached to the non-treated surface. Laminate.

Next, by using a belt conveyor type ultraviolet irradiation device (manufactured by EYE GRAPHICS, product name: ECS-401GX), under the conditions shown below, a high-pressure mercury lamp (manufactured by EYE GRAPHICS, "H04-L41 ”) and an ultraviolet light meter (“UV-351”, manufactured by Orc Manufacturing Co., Ltd.), irradiating ultraviolet rays through the step sheet to carry out a curing reaction, and forming a base layer with a thickness of 10 μm on the aforementioned first release sheet. <Conditions by high pressure mercury lamp> ‧Ultraviolet lamp height: 100mm ‧Ultraviolet lamp output: 3kW <Conditions by ultraviolet light meter> ‧Illuminance with light wavelength of 365nm: 400mW/cm ² ‧Light quantity: 800mJ/cm ²

(2) Step of forming the gas barrier layer <1st layer> Next, the polyethylene terephthalate (PET) film used as the step sheet was peeled off. Further, on the above-formed base layer, an inorganic polysilazane-based coating agent, which is a composition for a gas barrier layer, is applied by a solution method, that is, a spin coating method to form a coating film. Here, the aforementioned "inorganic polysilazane-based coating agent" is made by adjusting the xylene concentration of "AQUAMICA NL110-20 (main component: perhydropolysilazane)" manufactured by Merck Performance Materials Co., Ltd. to 20% solution. Furthermore, by heating the obtained coating film at 120° C. for 1 minute to dry the coating film, a polysilazane-based compound layer with a thickness of 100 nm was formed on the aforementioned base layer. Furthermore, on the surface of the polysilazane-based compound layer formed above, a plasma ion implantation apparatus (RF power source: "RF56000" manufactured by JEOL Ltd., high voltage pulse power source: "PV-3-HSHV- 0835"), under the conditions shown below, a modification treatment by plasma ion implantation was performed to form the first gas barrier layer. <Plasma ion implantation conditions> ‧Cavity pressure: 0.2Pa ‧Plasma generating gas: Argon ‧Gas flow rate: 100sccm ‧RF output: 1000W ‧RF frequency: 1000Hz ‧RF pulse width: 50μsec ‧RF delay: 25nsec‧ DC voltage: -10kV ‧DC frequency: 1000Hz ‧DC pulse width: 5μsec ‧DC delay: 50μsec ‧Duty ratio: 0.5% ‧Processing time (ion implantation time): 200 seconds A polysilazane-based compound layer with a thickness of 100 nm was formed on the gas barrier layer of the first layer of the reforming treatment by the same method as the formation of the gas barrier layer of the first layer described above. Furthermore, a modification treatment by plasma ion implantation is performed on the surface on which the polysilazane-based compound layer is formed in the same manner as the modification treatment of the gas barrier layer of the first layer described above to form a second layer. the gas barrier.

(3) Step of forming the adhesive layer An acid-modified polyolefin-based resin (manufactured by Mitsui Chemicals, Inc., "UNISTOLE H-200", α-olefin polymer, weight-average molecular weight (Mw) as the polyolefin-based resin (A) ): 52,000) 100 parts, 25 parts of polyfunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX8034", hydrogenated bisphenol A diglycidyl ether) as thermosetting component (B), and 25 parts of hardening catalyst ( C) 0.25 part of imidazole-based hardening catalyst (manufactured by Shikoku Chemicals Co., Ltd., "Curezol 2E4MZ", 2-ethyl-4-methylimidazole) was dissolved in methyl ethyl ketone to obtain a 18% solution with a solid content concentration to prepare the adhesive composition.

As the second release sheet, the adhesive composition prepared above was applied to the peeled surface of a polyethylene terephthalate (PET) film (manufactured by Lintec, "SP-PET382150") to a thickness after drying It was coated with a knife coater so as to be 25 μm to form a coating film. By heating the coating film at 100° C. for 2 minutes, the coating film was dried, and an adhesive layer with a thickness of 25 μm was formed on the aforementioned second release sheet. Next, on this adhesive layer, as a third release sheet, a release-treated surface of a polyethylene terephthalate (PET) film (manufactured by Lintec, "SP-PET381031") was attached and laminated. Then, the polyethylene terephthalate (PET) film used as the third release sheet was peeled off. Then, the surface of the exposed adhesive layer and the surface of the gas barrier layer of the second layer formed above were heated to 60° C. using a thermal laminator by overlapping the surface of the exposed adhesive layer, so that the second release sheet remained in the adhesive layer. On the gas barrier layer of the second layer, an adhesive layer with a thickness of 25 μm is formed, and the first release sheet/base layer/the gas barrier layer of the first layer (with modification)/the gas barrier layer of the second layer (with modification) is produced. The gas-barrier film of Example 1 was composed of the layer of the adhesive layer/adhesive layer/second release sheet.

[Fabrication of organic EL device] An indium tin oxide (ITO) film (thickness: 150 nm, sheet resistance: 30Ω/□) was formed on the surface of a glass substrate by sputtering, and then solvent cleaning and UV/ Ozone treatment to form the anode. On the anode (ITO film) formed above, as a material for forming the light-emitting layer, N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-phenylidene) ( Luminescence Technology Co., Ltd.) 60 nm, gins (8-hydroxy-quinolinate) aluminum (Luminescence Technology Co., Ltd.) 40 nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminescence Technology Co., Ltd.) 10 nm and (8-hydroxy-quinoline) lithium (manufactured by Luminescence Technology Co., Ltd.) 10 nm were sequentially vapor-deposited at a rate of 0.1 to 0.2 nm/s to form a light-emitting layer. On the light-emitting layer formed above, aluminum (Al) (manufactured by High Purity Chemical Laboratory Co., Ltd.) was vapor-deposited for 100 nm at a rate of 0.1 nm/s to form a cathode, and a layer structure having a glass substrate/anode/light-emitting layer/cathode was produced. of organic EL elements. Furthermore, in the production step of the organic EL device, the vacuum degree when the above-mentioned material for forming the light-emitting layer is sequentially vapor-deposited on the anode (ITO film) is set to be 1×10 ^-4 Pa or less.

[Preparation of Sealing Body] Next, the second release sheet was peeled and removed from the gas barrier film prepared in the above-mentioned Example 1, and the surface of the adhesive layer of the gas barrier film as a sealing material was exposed. Next, the surface of the exposed adhesive layer and the surface of the organic EL element to be the sealant produced above were superimposed and heated to 60° C. using a thermal laminator in a nitrogen atmosphere, while pressing the surface of the adhesive layer and the surface of the organic EL element. The surface edge of the organic EL element as the object to be sealed was bonded to produce a sealing body in which the organic EL element as the object to be sealed was sealed with a gas barrier film as a sealing material. Furthermore, the sealing body of Example 1 was produced by heating the sealing body produced above at 100°C for 2 hours to harden the adhesive layer.

(Comparative Example 1) In addition to the step of forming the adhesive layer in Example 1, a rubber-based adhesive (manufactured by Japan Butyl Corporation, "Exxon Butyl 268", number average molecular weight: 260,000, a copolymer of isobutylene and isoprene was added , isoprene content: 1.7 mol %) 100 parts and an adhesion imparting agent (manufactured by Japan Zeon, "Quinton A100") 20 parts were dissolved in toluene to prepare an adhesive composition so that the solid content concentration was 20% Other than that, it carried out similarly to Example 1, and produced the gas-barrier film of the comparative example 1. Furthermore, in the production of the sealing body of Example 1, the sealing body of Comparative Example 1 was produced in the same manner as in Example 1, except that the adhesive layer was not cured.

[Evaluation method] (1) Evaluation of gas barrier properties For each of the gas barrier films produced in Example 1 and Comparative Example 1, the second release sheet was removed by peeling off, and the first release sheet remained as a measurement sample. The water vapor transmission rate (g/m ² /day). Furthermore, the detection lower limit of the water vapor transmission rate measuring device is 0.0005 (g/m ² /day). From the results of the water vapor transmission rate (g/m ² /day) thus measured, the gas barrier properties of the gas barrier film were evaluated on the basis of the following two-stage criteria. A: Water vapor transmission rate is 5×10 ^-3 (g/m ² /day) or less B: Water vapor transmission rate exceeds 5×10 ^-3 (g/m ² /day)

(2) Evaluation of the sealing performance of the object to be sealed . After the sample for measurement was placed in a high temperature and high humidity environment of 40°C and a relative humidity of 90% for 100 hours, the organic EL element was activated, and the area of the non-luminescent area (dark spot) was measured, and the relative area of the non-luminescent area was calculated. The ratio (%) of the luminous area (100%) in the initial stage before placement. Furthermore, the sealing performance of the organic EL element as the sealing material to the sealing material of the gas-barrier film as the sealing material was evaluated using the four-stage standard shown below. A: The ratio of the area of the non-luminous area is less than 5% B: The ratio of the area of the non-luminous area is more than 5% and less than 10% C: The ratio of the area of the non-luminous area is more than 10% and less than 90% D: The area of the non-luminous area The proportion of the area where the light is emitted is more than 90%

[Table 1]

(Summary of Results) The following things are understood from the evaluation results shown in Table 1. In the production of the gas barrier film of Comparative Example 1, it was found that the adhesive layer was formed from an adhesive composition containing a rubber-based adhesive and an adhesion-imparting agent, and the sealed body of Comparative Example 1 was exposed to high temperature and high temperature for a long time. In a wet environment, the adhesiveness could not be maintained on the bonding surface of the adhesive layer of the sealing material and the object to be sealed, and the sealing performance of the gas barrier film of Comparative Example 1 to the object to be sealed was deteriorated.

In contrast, in the production of the gas barrier film of Example 1, it was found that the adhesive layer was formed from the adhesive composition containing the polyolefin-based resin (A) and the thermosetting component (B). When the sealing body of Example 1 is exposed to a high temperature and high humidity environment for a long time, it can also maintain excellent adhesion between the adhesive layer of the sealing material and the bonding surface of the object to be sealed. Excellent sealing performance.

Claims (14)

A gas-barrier film, which is a gas-barrier film having a laminate formed by laminating a release sheet, a base layer, a gas-barrier layer, and an adhesive layer in order, characterized in that the adhesive layer is composed of a polyolefin-containing It is a layer formed of the adhesive composition of the resin (A) and the thermosetting component (B). The gas barrier film according to claim 1, wherein the polyolefin-based resin (A) includes a modified polyolefin-based resin (A1). The gas barrier film according to claim 1 or 2, wherein the thermosetting component (B) contains a thermosetting epoxy resin (B1). The gas barrier film according to claim 1 or 2, wherein the adhesive layer is directly laminated on the gas barrier layer. The gas-barrier film according to claim 1 or 2, wherein the adhesive layer is laminated on the gas-barrier layer through an adhesion-enhancing layer. The gas barrier film according to claim 1 or 2, wherein the base layer is a layer formed of a composition for a base layer containing an energy ray curable component. The gas barrier film according to claim 1 or 2, wherein the base layer is a layer formed of a base layer composition further containing a thermoplastic resin. The gas barrier film according to claim 7, wherein the glass transition temperature (Tg) of the thermoplastic resin is 140°C or higher. The gas barrier film according to claim 1 or 2, wherein the base layer has a thickness of 0.1 to 10 μm. The gas-barrier film according to claim 1 or 2, wherein the gas-barrier layer contains a polysilazane-based compound and is formed by performing a modification treatment. The gas barrier film according to claim 1 or 2, wherein the polyolefin-based resin (A) is contained in a polymer composed of only repeating units of an olefin-based monomer derived from an α-olefin having 2 to 8 carbon atoms. The side chain of the modified polyolefin resin (A1) into which functional groups are introduced. The gas barrier film according to claim 1 or 2, wherein the adhesive composition further contains a hardening catalyst (C). A sealing body, which is sealed with a gas-barrier film as claimed in any one of claims 1 to 12, wherein the sealed material is selected from organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL elements At least one of the group consisting of an EL display element, an electronic paper element, a liquid crystal display element, and a solar cell element. A method for producing a sealing body, comprising the steps of adhering an adhesive layer of the gas barrier film according to any one of claims 1 to 12 to an object to be sealed, and peeling the peeling from the gas barrier film Steps for flakes.