Gas barrier multilayer film

Abstract

To provide a multilayer film which exhibits excellent moisture barrier properties.SOLUTION: There is provided a gas barrier multilayer film which comprises a base material layer (A1), a moisture trap layer (B1) and an outer layer (Q) in this order, wherein the base material layer (A1) has a layer selected from the group consisting of an inorganic barrier layer (a1) and an inorganic barrier layer (a2) on at least one surface of a plastic layer (x) and the base material layer (A1) has a moisture permeability (40°C, RH 90%) of less than 1×10-3 g / m2 / day.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a gas barrier multilayer film used as a sealing material or substrate for electronic devices such as organic electroluminescence (EL) elements and solar cells. [Background technology]

[0002] Various electronic devices that have been developed and put into practical use in recent years, such as organic electroluminescence (organic EL), solar cells, touch panels, and electronic paper, require high moisture barrier properties to prevent charge leakage due to moisture.

[0003] Incidentally, as a means for improving the properties of various plastic substrates, particularly their gas barrier properties, it is known to form an inorganic thin film (inorganic barrier layer) made of silicon oxide or the like on the surface of the plastic substrate by vapor deposition (Patent Document 1), and films with such inorganic thin films are widely used as barrier films. However, such barrier films are insufficient to satisfy the moisture barrier properties required for the above-mentioned electronic devices, and residual moisture in the resins used in the plastic substrates significantly deteriorates the devices.

[0004] To meet such demands, a moisture barrier laminate is also known which has a structure in which a moisture trapping layer having a hygroscopic ionic polymer as a matrix is ​​laminated (Patent Document 2).

[0005] The moisture-trapping layer as described above is formed by applying a coating composition for forming a trapping layer containing an ionic polymer onto an inorganic barrier layer formed on the surface of a plastic film by vapor deposition or the like, and then curing the composition. The formation of such a layer exhibits excellent moisture barrier properties.

[0006] However, since the inorganic barrier layer has insufficient moisture barrier properties, the moisture barrier properties are not yet sufficient for use as an encapsulant for electronic devices, and the problem remains unsolved. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-255579 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-96320 Summary of the Invention [Problem to be solved by the invention]

[0008] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a multilayer film that exhibits sufficient moisture barrier properties as an encapsulant for electronic devices. [Means for solving the problem]

[0009] The present invention includes the following inventions. 1. A fabric comprising a substrate layer (A1), a moisture-trapping layer (B1), and an outer layer (Q) in this order; The substrate layer (A1) has a layer selected from the group consisting of an inorganic barrier layer (a1) and an inorganic barrier layer (a2) on at least one surface of the plastic layer (x), the outer layer (Q) has a layer selected from the group consisting of the plastic layer (C), the base layer (A1) and the base layer (A2), the base layer (A2) is a layer having an inorganic barrier layer (a4) on one surface of a plastic layer (y), The aforementioned The moisture permeability of the base layer (A1) (40°C, RH90%) 2.0×10 -4 g / m 2 / day or less Yes the law of nature , The layer structure is as follows: Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a3) ​​ / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a1) / plastic layer (x), Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a4) / plastic layer (y), Plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a3) ​​ / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a1) / plastic layer (x), Either Gas barrier multilayer film. 2 The inorganic barrier layers (a1) to (a 4 ) is a metal oxide film 1 to The gas barrier multilayer film according to claim 1, 3 The plastic layers (x) to ( y ) refers to the above item 1, including olefin resin, polyester resin, polyimide resin, polyamide resin or cyclic olefin resin. or 2 The gas barrier multilayer film according to claim 1. 4 The moisture trapping layer (B1 )teeth The present invention relates to a resin composition comprising an ionic polymer (i) and a moisture absorbent (ii) dispersed therein, and 3 10. The gas barrier multilayer film according to claim 9, 5 The plastic layer (C) may contain an olefin resin, a polyester resin, a polyimide resin, a polyamide resin, or a cyclic olefin resin. 4 10. The gas barrier multilayer film according to claim 9, [Effects of the Invention]

[0010] The gas barrier multilayer film of the present invention has excellent moisture barrier properties. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional side view showing the layer structure of a multilayer film 1 of Example 1. FIG. [Figure 2] FIG. 2 is a schematic cross-sectional side view showing the layer structure of a multilayer film 2 of Example 2. [Figure 3] FIG. 3 is a schematic cross-sectional side view showing the layer structure of a multilayer film 3 of Example 3. [Figure 4]1 is a schematic cross-sectional side view showing the layer structure of a multilayer film 4 of Example 4. FIG. [Figure 5] FIG. 1 is a schematic cross-sectional side view showing the layer structure of a multilayer film 5 of Example 5. [Figure 6] 1 is a schematic cross-sectional side view showing the layer structure of a multilayer film 6 of Comparative Example 1. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0012] The multilayer film of the present invention comprises a substrate layer (A1), a moisture-trapping layer (B1), and an outer layer (Q) in this order, The substrate layer (A1) has a layer selected from the group consisting of an inorganic barrier layer (a1) and an inorganic barrier layer (a2) on at least one surface of the plastic layer (x), The moisture permeability of the base layer (A1) (40°C, RH90%) is 1 x 10 -3 g / m 2 / day or less, It is a gas barrier multilayer film.

[0013] <Base material layer (A1)> The substrate layer (A1) has a layer selected from the group consisting of an inorganic barrier layer (a1) and an inorganic barrier layer (a2) on at least one surface of the plastic layer (x).

[0014] <Plastic layer (x)> The plastic layer (x) is a base for the inorganic barrier layer (a1) and the inorganic barrier layer (a2) described later, and is usually made of a thermoplastic or thermosetting resin, and is molded by injection or co-injection molding, extrusion or co-extrusion molding, film or sheet molding, compression molding, or the like, depending on the form. shape, It is molded by cast polymerization or the like.

[0015] The plastic layer (x) is preferably formed of a thermoplastic resin from the viewpoints of moldability, cost, etc. Examples of such thermoplastic resins include low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene. comrades ethylene-vinyl compound copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl chloride copolymer; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymer, ABS, and α-methylstyrene-styrene copolymer; polyvinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polymethyl acrylate, and polymethyl methacrylate; polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12; thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN); polycarbonate; polyphenylene oxide; and biodegradable resins such as polyimide resin, polyamide-imide resin, polyetherimide resin, fluororesin, allyl resin, polyurethane resin, cellulose resin, polysulfone resin, polyethersulfone resin, ketone resin, amino resin, and polylactic acid. Furthermore, blends of these resins and resins modified by appropriate copolymerization (for example, acid-modified olefin resins) may also be used. The plastic layer (x) preferably contains an olefin resin, a polyester resin, a polyimide resin, a polyamide resin or a cyclic olefin resin.

[0016] It is also preferable that the plastic layer (x) is formed from a gas barrier resin having excellent oxygen barrier properties, such as an ethylene-vinyl alcohol copolymer, and furthermore, the plastic layer (x) may have a multilayer structure including a layer formed from such a gas barrier resin.

[0017] From the viewpoint that the plastic layer (x) is suitable as a base for the inorganic barrier layer (a) described below, it is more preferable to use a film of a polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate, or polyethylene naphthalene carboxylate, or a cyclic olefin resin such as a polyimide resin, a polyamide resin, or a cyclic olefin copolymer or a cyclic olefin polymer as the plastic layer (x).

[0018] Although the thickness of the plastic layer (x) is not particularly limited, if the thickness is too large, the residual moisture content of the plastic layer (x) increases, and the flexibility of the gas barrier multilayer film is lost. Therefore, the thickness of the plastic layer (x) is preferably 200 μm or less, more preferably 125 μm or less, and even more preferably 45 μm or less.

[0019] <Inorganic Barrier Layer (a1), Inorganic Barrier Layer (a2)> The substrate layer (A1) has an inorganic barrier layer on at least one side of the plastic layer (x). The substrate layer (A1) may be one of the following embodiments α, β, and γ. The embodiment α is an embodiment in which the substrate layer (A1) has an inorganic barrier layer (a1) on the surface opposite to the moisture-trapping layer (B1). The embodiment β is an embodiment in which the substrate layer (A1) has an inorganic barrier layer (a2) on the surface on the moisture-trapping layer (B1) side. The embodiment γ is an embodiment that includes the above-mentioned (α) and (β), that is, an embodiment in which the base layer (A1) has an inorganic barrier layer (a1) on the surface opposite to the moisture-trapping layer (B1), and an inorganic barrier layer (a2) on the surface facing the moisture-trapping layer (B1).

[0020] The inorganic barrier layer (a1) and the inorganic barrier layer (a2) may be layers having the same properties and thickness, or may be layers having different properties and thicknesses.

[0021] In the present invention, the moisture permeability (40°C, RH 90%) of the substrate layer (A1) is 1 × 10 -3 g / m 2 / day, preferably less than 8 × 10 -4 g / m 2 / day, preferably less than 5 × 10 -4 g / m 2 / day. When the base layer (A1) has an inorganic barrier layer (a1) or an inorganic barrier layer (a2) on one side of the plastic layer (x), the moisture permeability of the base layer (A1) (40°C, RH 90%) is preferably 1 × 10 -3 g / m 2 / day, more preferably less than 8×10 -4 g / m 2 / day, more preferably less than 5 × 10 -4 g / m 2 / day. When the base layer (A1) has an inorganic barrier layer (a1) on one side of the plastic layer (x) and an inorganic barrier layer (a2) on the other side, the moisture permeability of the base layer (A1) (40°C, RH 90%) is preferably 8 × 10 -4 g / m 2 / day, more preferably less than 5×10 -4 g / m 2 / day, more preferably less than 3 × 10 -4 g / m 2 / day.

[0022] The inorganic barrier layer (a1) and the inorganic barrier layer (a2) are each formed on a plastic layer (x) as a base. The inorganic barrier layer (a) is preferably a film formed by vapor deposition or wet coating. Vapor deposition includes inorganic or inorganic-organic hybrid vapor deposition films formed by physical vapor deposition such as sputtering, vacuum deposition, and ion plating, and chemical vapor deposition such as plasma CVD. Wet coating includes inorganic or inorganic-organic hybrid coating films formed by a sol-gel process. The inorganic barrier layer (a1) and the inorganic barrier layer (a2) are preferably films formed from various metals, metal oxides, or metal oxides containing organic substances, in order to ensure high oxygen barrier properties. In particular, they are preferably formed by plasma CVD or a sol-gel process, in order to be uniformly formed on uneven surfaces and to exhibit excellent barrier properties against not only oxygen but also moisture. The inorganic barrier layer (a1) and the inorganic barrier layer (a2) are preferably metal oxide films or metal oxides containing organic substances.

[0023] The deposited film by plasma CVD is obtained by placing a film-form plastic layer (x) that serves as the base for the inorganic barrier layer (a1) and the inorganic barrier layer (a2) in a plasma processing chamber maintained at a predetermined vacuum level, and supplying a gas (reactive gas) of the metal or a compound containing the metal to be used to form the film and an oxidizing gas (usually oxygen or NOx gas) together with an appropriate carrier gas such as argon or helium using a gas supply pipe into the plasma processing chamber, which is shielded by a metal wall and has been reduced to a predetermined vacuum level, and generating a glow discharge in this state using a microwave electric field, a high-frequency electric field, or the like, generating plasma using the electrical energy generated, and depositing the decomposition reaction products of the compound on the surface of the plastic layer (x) to form a film.

[0024] As the above-mentioned reactive gas, it is generally preferable to use a gas such as an organometallic compound, for example, an organoaluminum compound such as trialkylaluminum, an organotitanium compound, an organozirconium compound, or an organosilicon compound, from the viewpoint of being able to form a film having a flexible region containing a carbon component at the interface with the underlying plastic layer (x) and having a region thereon with a high degree of oxidation and excellent barrier properties. In particular, organosilicon compounds are most preferable from the viewpoint of being able to relatively easily and efficiently form the inorganic barrier layer (a1) or inorganic barrier layer (a2) with high barrier properties against oxygen.

[0025] Examples of such organosilicon compounds include organosilane compounds such as hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane, as well as organosiloxane compounds such as octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, and hexamethyldisiloxane. In addition to these, aminosilanes and silazanes can also be used. The above-mentioned organometallic compounds can be used alone or in combination of two or more.

[0026] The thickness of the inorganic barrier layer (a1) and the inorganic barrier layer (a2) is set to a value that satisfies a predetermined moisture permeability depending on the thickness of the underlying plastic layer (x), and generally ranges from 4 to 500 nm, and particularly from 30 to 400 nm.

[0027] Furthermore, the inorganic barrier layer (a1) and the inorganic barrier layer (a2) can also be formed on the plastic layer (x) by coating or the like, rather than by a method such as vapor deposition.

[0028] The inorganic barrier layer (a) formed by coating is typically formed by using an organic solvent solution containing polysilazane, a polycondensable silane compound (e.g., alkoxysilane), or a polycondensable alumina compound (e.g., alkoxyaluminum) as a film-forming component, optionally mixed with inorganic fine particles such as silica or alumina, which is applied to a predetermined surface, heated, and the organic solvent is evaporated to form a film.

[0029] The inorganic barrier layer (a) may have an anchor coat layer and a top coat layer. The anchor coat layer and the top coat layer can be formed using known techniques. For example, acrylic resin, epoxy resin, acrylic urethane resin, polyester polyurethane resin, or polyether polyurethane resin can be used for the anchor coat layer. From the viewpoints of adhesion and heat resistance, polyester polyurethane resin and acrylic urethane resin are preferred. For example, polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, carboxymethyl cellulose, starch, sodium alginate, or a mixture thereof can be used for the top coat layer. For the top coat layer, inorganic oxides can be mixed with the above resins.

[0030] <Outer layer (Q)> When the multilayer film of the present invention is attached to an electronic device, the outer layer (Q) is the layer on the side opposite to the electronic device. The outer layer (Q) is a layer selected from the group consisting of a plastic layer (C), a substrate layer (A1), and a substrate layer (A2). In the present invention, there is an embodiment in which the same layer as the substrate layer (A1) is used as the outer layer (Q). That is, there is an embodiment in which two layers of the same substrate layer (A1) are used. The substrate layer (A2) and the plastic layer (C) will be described later.

[0031] <Base material layer (A2)> The base layer (A2) has an inorganic barrier layer (a4) on one side of the plastic layer (y). In the present invention, as shown in (7) and (8) of embodiment γ described below, the moisture-trapping layer (B1) may further include an adhesive layer (D) and a base layer (A2) in this order on the surface opposite to the base layer (A1). The material and thickness of the plastic layer (y) can be the same as those described in the section on the plastic layer (x). The material and thickness of the plastic layer (y) may be the same as or different from those of the plastic layer (x). The characteristics, material, thickness, and manufacturing method of the inorganic barrier layer (a4) can be the same as those of the inorganic barrier layer (a1) and the inorganic barrier layer (a2). The characteristics, material, thickness, and manufacturing method of the inorganic barrier layer (a4) may be the same as or different from those of the inorganic barrier layer (a1) or the inorganic barrier layer (a2). The moisture permeability (40°C, RH 90%) of the inorganic barrier layer (a4) is not necessarily 1×10 -3 g / m 2 It does not have to be less than / day.

[0032] <Base material layer (A3)> The base layer (A3) has an inorganic barrier layer (a5) on one side of the plastic layer (z). In the present invention, as shown in (5) to (8) and (11) to (12) of Aspect γ described below, the moisture-trapping layer (B2) further includes an adhesive layer (D) and a substrate layer (A3) in this order on the side opposite the substrate layer (A1), and the substrate layer (A3) can have an inorganic barrier layer (a5) on one side of the plastic layer (z). Aspect γ (6) is an aspect in which the substrate layer (A3) in Aspect γ (5) is inverted. Aspect γ (8) is an aspect in which the substrate layer (A3) in Aspect γ (7) is inverted.

[0033] The material and thickness of the plastic layer (z) can be the same as those described in the section on the plastic layer (x). The material and thickness of the plastic layer (z) may be the same as or different from those of the plastic layer (x). The characteristics, material, thickness, and manufacturing method of the inorganic barrier layer (a5) can be those described in the sections for the inorganic barrier layer (a1) and the inorganic barrier layer (a2). The characteristics, material, thickness, and manufacturing method of the inorganic barrier layer (a5) may be the same as or different from those of the inorganic barrier layer (a1) or the inorganic barrier layer (a2). The moisture permeability (40°C, RH 90%) of the inorganic barrier layer (a5) is not necessarily 1×10 -3 g / m 2 It does not have to be less than / day.

[0034] <Inorganic barrier layer (a3)> The multilayer film of the present invention may have an embodiment containing an inorganic barrier layer (a3), an inorganic barrier layer (a4) and an inorganic barrier layer (a5) other than the inorganic barrier layer (a1) and the inorganic barrier layer (a2) constituting the base layer (A1). The inorganic barrier layer (a3) ​​is a layer formed on the plastic layer (C) as a base. The inorganic barrier layer (a3) ​​can be formed on the surface of the plastic layer (C) on the moisture-trapping layer (B1) side.

[0035] The inorganic barrier layer (a3) ​​may be made of the same material as the inorganic barrier layer (a1) or the inorganic barrier layer (a2) and may have the same thickness. The inorganic barrier layer (a3) ​​can be formed by the same method as the inorganic barrier layer (a1) or the inorganic barrier layer (a2). a3 ) may have an anchor coat layer and a top coat layer. The anchor coat layer and the top coat layer can be formed using known techniques. For example, acrylic resin, epoxy resin, acrylic urethane resin, polyester polyurethane resin, or polyether polyurethane resin can be used for the anchor coat layer. From the viewpoint of adhesion and heat resistance, polyester polyurethane resin and acrylic urethane resin are preferred. For example, polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, carboxymethyl cellulose, starch, sodium alginate, or a mixture thereof can be used for the top coat layer. For the top coat layer, inorganic oxides can be mixed with the above resins.

[0036] <Moisture trapping layer (B1)> In the present invention, the moisture-trapping layer (B1) serves to block moisture from flowing in the thickness direction of the gas barrier multilayer film.

[0037] <Ionic polymer> The moisture-trapping layer (B1) is preferably formed from an ionic polymer. The moisture-trapping layer (B1) is preferably formed by using an ionic polymer as a matrix and dispersing a moisture-absorbing agent having a lower humidity level than the ionic polymer in the matrix. Such a layer having an ionic polymer as a matrix has excellent moisture-trapping properties, and a layer having a moisture-absorbing agent having a lower humidity level dispersed therein can transfer the moisture absorbed by the ionic polymer to the moisture-absorbing agent, thereby trapping the absorbed moisture within the moisture-absorbing agent, and completely trapping the permeated moisture within the trapping layer. capture In addition, deformation such as swelling caused by moisture absorption in the trap layer can be effectively avoided.

[0038] Ionic polymers suitable for use in forming the moisture-trapping layer (B1) include cationic polymers and anionic polymers.

[0039] A cationic polymer is a polymer having, in its molecule, a cationic group that can become positively charged in water, such as a primary to tertiary amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, or a quaternary pyridinium group. Such cationic polymers have a cationic group that has a strong nucleophilic action and can attract water by hydrogen bonding. capture Therefore, a hygroscopic matrix can be formed. The amount of cationic groups in the cationic polymer is generally sufficient if the water absorption rate (JISK-7209-1984) of the polymer is 20% or more, particularly 30 to 45%, in an atmosphere of 80% RH and 30°C.

[0040] The cationic polymer is obtained by polymerizing or copolymerizing at least one cationic monomer, such as an amine monomer (e.g., allylamine, ethyleneimine, vinylbenzyltrimethylamine, [4-(4-vinylphenyl)-methyl]-trimethylamine, or vinylbenzyltriethylamine), a nitrogen-containing heterocyclic monomer (e.g., vinylpyridine or vinylimidazole), or a salt thereof, together with other copolymerizable monomers, and then, if necessary, partially neutralizing the polymer by acid treatment. Polyallylamine is a suitable cationic polymer from the viewpoint of film-forming properties, etc.

[0041] On the other hand, anionic polymers are polymers that have anionic functional groups that can become negatively charged in water, such as carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, or acidic bases formed by partially neutralizing these groups, in the molecule. Anionic polymers with such functional groups have the ability to attract water by hydrogen bonding. capture Therefore, a hygroscopic matrix can be formed. The amount of anionic functional groups in the anionic polymer varies depending on the type of functional group, but similar to the cationic polymer described above, it is sufficient that the water absorption rate (JISK-7209-1984) of the polymer is 20% or more, particularly 30 to 45%, in an atmosphere of 80% RH and 30°C.

[0042] Examples of anionic polymers having such functional groups include those obtained by polymerizing or copolymerizing at least one anionic monomer, such as carboxylic acid monomers (e.g., methacrylic acid, acrylic acid, maleic anhydride), sulfonic acid monomers (e.g., α-halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid), phosphonic acid monomers (e.g., vinyl phosphoric acid), and salts of these monomers, together with other copolymerizable monomers, and, if necessary, partially neutralizing the resulting polymer by alkali treatment. Poly(meth)acrylic acid and its partially neutralized products (e.g., those partially containing sodium salts) are preferred as anionic polymers.

[0043] <Moisture absorbent> The moisture absorbent can transfer moisture absorbed by the ionic polymer to the moisture absorbent, trapping the absorbed moisture within the moisture absorbent. It can also prevent deformation due to swelling of the ionic polymer. The moisture absorbent preferably has a lower ultimate humidity than the ionic polymer. Examples of such moisture absorbents include those with an ultimate humidity of 6% or less under environmental conditions of 80% RH and 30°C. That is, if the ultimate humidity of the moisture absorbent is higher than that of the ionic polymer, the moisture absorbed in the matrix is ​​not sufficiently trapped, making it more likely to release moisture. However, when a moisture absorbent with a lower ultimate humidity than the ionic polymer is incorporated into the ionic polymer, not only can moisture be effectively trapped even in a low-humidity atmosphere, but the moisture absorbed by the ionic polymer can also be captured by the moisture absorbent, thereby suppressing moisture release and providing high moisture barrier properties.

[0044] Moreover, the moisture absorbents described above generally have a water absorption rate of 50% or more (JISK-7209-1984) in an atmosphere of 80% RH humidity and 30° C. temperature, and are available in inorganic and organic types. Examples of inorganic moisture absorbents include zeolite, alumina, activated carbon, clay minerals such as montmorillonite, silica gel, calcium oxide, and magnesium sulfate. Examples of organic moisture absorbents include crosslinked anionic polymers or partially neutralized products thereof. Examples of such anionic polymers include those obtained by polymerizing or copolymerizing with other monomers at least one anionic monomer, such as a carboxylic acid monomer (e.g., (meth)acrylic acid or maleic anhydride), a sulfonic acid monomer (e.g., halogenated vinyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid), a phosphonic acid monomer (e.g., vinyl phosphoric acid), or a salt of one of these monomers. Organic moisture absorbents are particularly effective for applications requiring transparency. For example, fine particles of crosslinked sodium poly(meth)acrylate are a typical organic moisture absorbent.

[0045] Among the above moisture absorbents, those with small particle diameters are preferred (for example, those with an average primary particle diameter of 100 nm or less, particularly 80 nm or less) from the viewpoint of increasing the specific surface area and exhibiting high moisture absorption properties, and organic polymer moisture absorbents with small particle diameters are particularly optimal. That is, the organic polymer moisture absorbent has extremely good dispersibility in the ionic polymer matrix, and can be uniformly dispersed. Furthermore, by employing emulsion polymerization, suspension polymerization or the like as the polymerization method for producing the organic polymer moisture absorbent, the particle shape can be made to be fine and uniformly spherical, and by blending a certain amount of this, it becomes possible to ensure extremely high transparency.

[0046] Furthermore, organic fine moisture absorbents not only achieve the aforementioned extremely low humidity and exhibit high moisture absorption, but also can minimize volume change due to swelling through crosslinking, and are therefore optimal for reducing the humidity of the ambient atmosphere to an absolute dry state or close to an absolute dry state while suppressing volume change. As an example of such organic moisture absorbent particles, cross-linked sodium polyacrylate particles (average particle diameter: approximately 70 nm) are sold in the form of a colloidal dispersion (pH = 10.4) by Nippon Exlan Kogyo Co., Ltd. under the product name Tuftic HU-820E.

[0047] In the present invention, the amount of the moisture absorbent as described above is set according to the type of ionic polymer, from the perspective of fully exhibiting its properties, significantly improving the moisture barrier property, and effectively suppressing dimensional changes due to swelling, while at the same time ensuring a moisture barrier property that is higher for a long period of time than the barrier property exhibited by all of the inorganic barrier layers present in the gas barrier laminate. For example, when the moisture-trapping layer (B1) is formed by dispersing the moisture absorbent in a cationic polymer, it is generally present in an amount of 50 parts by weight or more, particularly 100 to 900 parts by weight, and more preferably 200 to 600 parts by weight, per 100 parts by weight of the cationic polymer. When the moisture absorbent is dispersed in an anionic polymer, it is present in an amount of 50 parts by weight or more, particularly 100 to 1300 parts by weight, and more preferably 150 to 1200 parts by weight, per 100 parts by weight of the anionic polymer.

[0048] <Crosslinking agent> In addition, in the moisture-trapping layer (B1) formed using the above-mentioned ionic polymer, it is preferable that a crosslinked structure is introduced into the ionic polymer. That is, if a crosslinked structure is introduced into the ionic polymer, when the ionic polymer absorbs water, the molecules of the ionic polymer are bound to each other by the crosslinks, which suppresses volume changes due to swelling (water absorption) and leads to improved mechanical strength and dimensional stability. Such a crosslinked structure can be introduced by incorporating a crosslinking agent into the coating composition for forming the moisture-trapping layer (B1). In particular, in the case of anionic polymers, unlike cationic polymers, the crosslinked structure is formed by hydrogen bonding. capture Therefore, by introducing a network structure (crosslinked structure) of spaces suitable for moisture absorption into the matrix, its moisture absorption properties can be greatly improved.

[0049] The crosslinking agent for introducing such a crosslinked structure differs slightly between when a crosslinked structure is introduced into a cationic polymer and when a crosslinked structure is introduced into an anionic polymer.

[0050] As a crosslinking agent for a cationic polymer, a compound having a crosslinkable functional group (e.g., an epoxy group) that can react with a cationic group and a functional group (e.g., an alkoxysilyl group) that can form a siloxane structure in the crosslinked structure through hydrolysis and dehydration condensation can be used. Specifically, a silane compound represented by the following formula (1) is preferably used. X-SiR1 n (OR 2 ) 3-n (1) In the formula, X is an organic group having an epoxy group at the end, and R 1 and R 2 are each independently a methyl group, an ethyl group, or an isopropyl group, and n is 0, 1, or 2.

[0051] Such silane compounds have epoxy and alkoxysilyl functional groups, and the epoxy groups undergo an addition reaction with the functional groups (e.g., NH) of the cationic polymer. Meanwhile, the alkoxysilyl groups generate silanol groups (SiOH groups) through hydrolysis, which then undergo a condensation reaction to form a siloxane structure and grow, ultimately forming a crosslinked structure between the cationic polymer chains. This results in a crosslinked structure containing a siloxane structure being introduced into the cationic polymer matrix. Moreover, the cationic polymer is alkaline, and as a result, it is difficult to form a moisture-trapping layer ( B1 When forming the silanol group, the addition reaction between the cationic group and the epoxy group and the dehydration condensation between the silanol groups are rapidly promoted, making it possible to easily introduce a crosslinked structure.

[0052] In the present invention, the organic group X having an epoxy group in the above formula (1) is typically a γ-glycidoxyalkyl group, and for example, γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropylmethyldimethoxysilane is preferably used as a crosslinking agent. In addition, compounds in which the epoxy group in the above formula (1) is an alicyclic epoxy group such as an epoxycyclohexyl group are also suitable as crosslinking agents. For example, when a compound having an alicyclic epoxy group such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is used as a crosslinking agent, an alicyclic structure is introduced into the crosslinked structure of the matrix together with the siloxane structure. The introduction of such an alicyclic structure can more effectively exert the matrix's function of forming a network structure with spaces suitable for moisture absorption.

[0053] Furthermore, in order to introduce an alicyclic structure into the above-mentioned crosslinked structure, a compound having a plurality of epoxy groups and an alicyclic group, for example, a diglycidyl ester represented by the following formula (2), can be used as a crosslinking agent. GO(C=O)-A-(C=O)OG (2) In the formula, G is a glycidyl group, and A is a divalent hydrocarbon group having an aliphatic ring, such as a cycloalkylene group.

[0054] A representative example of such a diglycidyl ester is represented by the following formula (2-1). [ka]

[0055] That is, although the diglycidyl ester of formula (2) does not have an alkoxysilyl group, it is effective in that it introduces an alicyclic structure into the crosslinked structure, thereby forming a network structure of spaces suitable for moisture absorption in the matrix.

[0056] The above-mentioned crosslinking agent is preferably used in an amount of 5 to 60 parts by weight, particularly 15 to 50 parts by weight, per 100 parts by weight of the cationic polymer, and it is desirable that at least 70% by weight, preferably 80% by weight or more of such crosslinking agent be the silane compound of formula (1) described above.

[0057] Furthermore, as a crosslinking agent for introducing a crosslinked structure into an anionic polymer, a compound having two or more crosslinkable functional groups (e.g., epoxy groups) capable of reacting with the ionic groups of the anionic polymer can be used, as described in JP 2015-96320 A. For example, a diglycidyl ester represented by formula (2), which is also mentioned in the coating composition for cationic matrices, is preferably used. GO(C=O)-A-(C=O)OG (2) In the formula, G is a glycidyl group, and A is a divalent hydrocarbon group having an aliphatic ring, such as a cycloalkylene group.。

[0058] That is, in the diglycidyl ester of the above formula (2), the epoxy group reacts with the anionic group, and a crosslinked structure containing an alicyclic structure is formed in the matrix by the divalent group A. The formation of such a crosslinked structure containing an alicyclic structure results in the suppression of swelling. In particular, the diglycidyl esters described above are suitable, and the diglycidyl ester represented by the formula (2-1) is the most suitable, from the viewpoint of forming a network structure of spaces suitable for moisture absorption. The moisture-trapping layer (B1) may have an anchor coat layer and a top coat layer. The anchor coat layer and the top coat layer can be formed using known techniques. The layer forming the anchor coat layer is, for example, an organic layer composed of at least one resin selected from urethane-based resins, polyester-based resins, polyether-based resins, epoxy-based resins, acrylic-based resins, phenol-based resins, and melamine-based resins, preferably formed from urethane resins, epoxy resins, or acrylic resins. A crosslinked structure may be introduced into these resins. Furthermore, the organic layer may contain an inorganic filler or a silane-based compound to improve barrier properties. The layer forming the top coat layer is, for example, an organic layer composed of at least one resin selected from urethane-based resins, polyester-based resins, polyether-based resins, epoxy-based resins, acrylic resins, phenol-based resins, and melamine-based resins, preferably formed from urethane resins, epoxy resins, or acrylic resins. A crosslinked structure may be introduced into these resins. Furthermore, the organic layer may contain a metal oxide to adjust the refractive index, an inorganic filler to improve barrier properties, or a silane-based compound to improve barrier properties.

[0059] Like this Anionic Polymers The crosslinking agent is preferably used in an amount of 1 to 50 parts by weight, particularly 10 to 40 parts by weight, per 100 parts by weight of the anionic polymer.

[0060] The moisture-trapping layer (B1) is formed by applying a coating composition in which a predetermined hygroscopic polymer or moisture absorbent is dissolved or dispersed in an organic solvent, heating the coating to form a film, and then holding the film in a dry atmosphere under reduced pressure to release moisture present in the formed layer. Alternatively, the moisture-trapping layer (B1) can be formed by applying the coating composition as described above to another organic film in the same manner, and then bonding the moisture-trapping layer (B1) to the substrate layer (A1) using a dry laminating adhesive or the like.

[0061] <Moisture trapping layer (B2)> In the present invention, the substrate layer (A1) may further include a moisture-trapping layer (B2) on the surface opposite to the moisture-trapping layer (B1), as shown in (3), (4), (6), and (8) of embodiment α, (3), (4), (6), and (8) of embodiment β, and (3) to (8), (11) to (12) of embodiment γ, which will be described later. The moisture-trapping layer (B2) is not particularly limited as long as it exhibits moisture-blocking properties, and may be a known layer, such as a layer in which a moisture absorbent such as zeolite is dispersed in a specific resin layer. The moisture-trapping layer (B2) may also be made of the same material as the moisture-trapping layer (B1). Both the moisture-trapping layer (B1) and the moisture-trapping layer (B2) preferably contain a resin composition in which a moisture absorbent (ii) is dispersed in a cationic polymer (i).

[0062] The moisture-trapping layer (B2) may have an anchor coat layer and a top coat layer. The anchor coat layer and the top coat layer can be formed using known techniques. The layer forming the anchor coat layer is, for example, an organic layer composed of at least one resin selected from urethane-based resins, polyester-based resins, polyether-based resins, epoxy-based resins, acrylic-based resins, phenol-based resins, and melamine-based resins, preferably composed of urethane resins, epoxy resins, or acrylic resins. A crosslinked structure may be introduced into these resins. Furthermore, the organic layer may contain an inorganic filler or a silane-based compound to improve barrier properties. The layer forming the top coat layer is, for example, an organic layer composed of at least one resin selected from urethane-based resins, polyester-based resins, polyether-based resins, epoxy resins, acrylic resins, phenol-based resins, and melamine-based resins, preferably composed of urethane resins, epoxy resins, or acrylic resins. A crosslinked structure may be introduced into these resins. Furthermore, the organic layer may contain a metal oxide to adjust the refractive index, an inorganic filler to improve barrier properties, or a silane-based compound to improve barrier properties.

[0063] <Plastic layer (C)> The plastic layer (C) can be a layer of the material and thickness described in the section on the plastic layer (x) above. The plastic layer (C) may be made of the same material as the plastic layer (x) above or a different material. The plastic layer (C) may have the same thickness as the plastic layer (x) above or a different thickness. The plastic layer (C) preferably contains an olefin resin, a polyester resin, a polyimide resin, a polyamide resin, or a cyclic olefin resin.

[0064] <Adhesive layer (D)> The multilayer film of the present invention preferably further comprises an adhesive layer (D) on the surface of the moisture-trapping layer (B1) on the side of the plastic layer (C).

[0065] Known adhesives such as (meth)acrylic adhesives and urethane adhesives can be used for the adhesive layer (D), and these adhesives can be used to form an adhesive layer (D) of a certain thickness or less (e.g., 30 μm or less). Ethylene-vinyl acetate copolymer (EVA), soft polyolefin (LLDPE), metallocene polyolefin elastomers, etc. can also be used as adhesives.

[0066] The adhesive is preferably adjusted so that its adhesive strength to the surface of the moisture-trapping layer (B1) is 0.3 N / 25 mm or more. The adhesive strength can be adjusted by introducing a crosslinked structure into the polymer forming the adhesive, depending on the material of the surface of the moisture-trapping layer (B1). The adhesive strength can also be adjusted by adding a lubricant or the like to the adhesive.

[0067] <Manufacturing of multilayer films> The multilayer film of the present invention comprises: (1) forming a layer selected from the group consisting of an inorganic barrier layer (a1) and an inorganic barrier layer (a2) by vapor deposition on at least one surface of the plastic layer (x) to form a substrate layer (A1); (2) a step of coating the base layer (A1) with a resin composition for forming the moisture-trapping layer (B1) and then curing the coating; and (3) coating the resulting multilayer film with an adhesive to form the adhesive layer (D), and then laminating the outer layer (Q); It can be produced by The plastic layer (x), vapor deposition, inorganic barrier layer (a), substrate layer (A1), moisture trapping layer (B1), adhesive layer (D), and outer layer (Q) are as described above.

[0068] <Application> The multilayer film of the present invention is used as an encapsulant for electronic devices. For example, the multilayer film can be attached to a device using a pressure-sensitive adhesive or the like to seal the device, thereby keeping the inside of the device dry. Alternatively, the multilayer film of the present invention can be used as a substrate for an electronic device, for example, by directly laminating an electronic device on the multilayer film of the present invention. The electronic device to which the multilayer film of the present invention is applied is not particularly limited, and the multilayer film can be applied to various electronic devices, such as organic EL elements, solar cells, touch panels, electronic panels, and other organic devices that are particularly susceptible to charge leakage due to moisture.

[0069] <Layer configuration> The substrate layer (A1) has the following aspects. Mode α: This mode has an inorganic barrier layer (a1) on the surface opposite to the moisture-trapping layer (B1). Mode β: A mode in which an inorganic barrier layer (a2) is provided on the surface on the moisture-trapping layer (B1) side. Aspect γ: A mode that combines the above-mentioned modes (α) and (β), i.e., a mode that has an inorganic barrier layer (a1) on the surface opposite the moisture-trapping layer (B1) and an inorganic barrier layer (a2) on the surface facing the moisture-trapping layer (B1).

[0070] Examples of layer configurations of the multilayer film of the present invention when using the base layer (A1) of embodiment α are as follows: Examples of outer layers (Q) include plastic layers (C) (1) to (4), base layers (A1) (5) to (6), i.e., a1 / x, and base layers (A2) (7) to (8), i.e., a4 / y. (1) a1 / x / B1 / D / C (2) a1 / x / B1 / D / a3 / C (3) B2 / a1 / x / B1 / D / C (4) B2 / a1 / x / B1 / D / a3 / C (5) a1 / x / B1 / D / a1 / x (6) B2 / a1 / x / B1 / D / a1 / x (7) a1 / x / B1 / D / a4 / y (8) B2 / a1 / x / B1 / D / a4 / y

[0071] Examples of layer configurations of the multilayer film of the present invention when using the base layer (A1) of embodiment β are as follows: Examples of the outer layer (Q) include plastic layers (C) (1) to (4), base layer (A1) (5) to (6), i.e., a1 / x, and base layer (A2) (7) to (8), i.e., a4 / y. (1) x / a2 / B1 / D / C (2) x / a2 / B1 / D / a3 / C (3) B2 / x / a2 / B1 / D / C (4) B2 / x / a2 / B1 / D / a3 / C (5) x / a2 / B1 / D / a1 / x (6) B2 / x / a2 / B1 / D / a1 / x (7) x / a2 / B1 / D / a4 / y (8) B2 / x / a2 / B1 / D / a4 / y

[0072] An example of the layer structure of the multilayer film of the present invention when using the base layer A of embodiment γ is as follows: The outer layer (Q) is made up of the plastic layers (C) (1) to (6), the base layer (A2) (7) to (8), i.e., a4 / y, (9) to ( 12 ) as the base layer (A1), ie, a1 / x. (1) a1 / x / a2 / B1 / D / C (2) a1 / x / a2 / B1 / D / a3 / C (3) B2 / a1 / x / a2 / B1 / D / C (4) B2 / a1 / x / a2 / B1 / D / a3 / C (5) a5 / z / D / B2 / a1 / x / a2 / B1 / D / C (6) z / a5 / D / B2 / a1 / x / a2 / B1 / D / C (7) a5 / z / D / B2 / a1 / x / a2 / B1 / D / a4 / y (8)z / a5 / D / B2 / a1 / x / a2 / B1 / D / a4 / y (9) a1 / x / a2 / B1 / D / a1 / x (10) B2 / a1 / x / a2 / B1 / D / a1 / x (11)a5 / z / D / B2 / a1 / x / a2 / B1 / D / a1 / x (12)z / a5 / D / B2 / a1 / x / a2 / B1 / D / a1 / x

[0073] In the above layer structure, the abbreviations are as follows: A1: Base layer (a1 / x, x / a2 or a1 / x / a2) A2: Base material layer (A4 / Y) A3: Base layer (a5 / z or z / a5) x: plastic layer y: plastic layer z: plastic layer a1: inorganic barrier layer a2: inorganic barrier layer a3: inorganic barrier layer A4: inorganic barrier layer A5: inorganic barrier layer B1: Moisture trapping layer B2: Moisture trapping layer C: Plastic layer

[0074] The multilayer film of the present invention is not limited to the layer structure described above, and for example, a plurality of multilayer films having the layer structure described above can be bonded to each other. [Example]

[0075] The excellent performance of the gas barrier multilayer film (multilayer film) of the present invention can be summarized as follows: Example This is explained below.

[0076] < Moisture permeability (g / m 2 / day) Measurement The water vapor permeability measurement device "HiBarSens 2.0 (SEMPA, Germany)" was used to measure under conditions of a temperature of 40°C and a relative humidity of 90%. The device switches the measurement mode depending on the barrier performance of the sample. -4 g / m 2 / day or more, the water vapor transmission rate is measured using the Carrier Gas mode, and the -4 g / m 2 Measurements of less than 1000 kJ / day were carried out in Combination mode, which is suitable for more sensitive measurements, in order to accurately evaluate high barrier performance.

[0077] <Coating Solution A preparation > Polyallylamine (manufactured by Nittobo Medical, PAA-15C, aqueous solution, solids content 15%) was used as an ionic polymer and diluted with water to a solids content of 5 wt % to obtain a polymer solution. Meanwhile, γ-glycidoxypropyltrimethoxysilane was used as a crosslinking agent and dissolved in water to a solids content of 5 wt % to prepare a crosslinking agent solution. Next, the polymer solution and the crosslinking agent solution were mixed so that 100 parts by weight of polyallylamine and 15 parts by weight of γ-glycidoxypropyltrimethoxysilane were mixed. Furthermore, a crosslinked product of sodium polyacrylate (manufactured by Nippon Exlan Kogyo, Tuftic HU-820E, aqueous dispersion, solids content 13%, average particle size D ) was added to this mixed solution as a granular moisture absorbent. 50 :70nm) was added to the polyallylamine so that the amount was 400 parts by weight, and the solid content was adjusted to 5% with water, followed by thorough stirring to prepare coating solution A for the moisture-trapping layer.

[0078] Example 1 A 100 μm thick biaxially stretched PET (polyethylene terephthalate) film was used as the plastic layer (x) (x in Figure 1), and an inorganic barrier layer (a1) (a1 in Figure 1) of silicon oxide was formed on one side of it using a plasma CVD apparatus to obtain a substrate layer (A1) (A1 in Figure 1). The film formation conditions are shown below.

[0079] Frequency 27.12MHz High-frequency oscillator A CVD apparatus was used, equipped with a matching box, a metal cylindrical plasma processing chamber with a diameter of 300 mm and a height of 450 mm, and an oil rotary vacuum pump for evacuating the processing chamber. A plastic substrate was placed on parallel flat plates in the processing chamber, and 3 sccm of hexamethyldisiloxane and 45 sccm of oxygen were introduced. A high-frequency oscillator was then oscillated at 50 W output to form a film for 2 seconds, forming an adhesive layer. Next, a high-frequency oscillator was oscillated at 500 W output to form a film for 30 seconds, forming an inorganic barrier layer (a1). The resulting inorganic barrier layer-coated PET film, the substrate layer (A1) (A1 in Figure 1), was measured in an atmosphere of 40°C and 90% RH. Moisture permeability But 2×10 -4 g / m 2 It was / day.

[0080] Under the conditions described above preparation The prepared coating solution A was applied using a bar coater to the PET surface of the base layer (A1) (A1 in Figure 1) having the inorganic barrier layer (a1) previously prepared. The coated film was then heat-treated in a box-type electric oven at a peak temperature of 120°C and a peak temperature holding time of 10 seconds to form a 4 μm-thick moisture-trapping layer (B1) (B1 in Figure 1), yielding a coating film (i) (11 in Figure 1).

[0081] The resulting coating film (i) was then quickly transferred into a glove box with a nitrogen concentration adjusted to 99.95% or higher. A 12-μm-thick industrial PET film was used as the plastic layer (C) (C in Figure 1), which was then dry-laminated onto the moisture-trapping layer (B1) (B1 in Figure 1) of the coating film (i) via a 4-μm-thick urethane adhesive layer (D) (D in Figure 1). To harden the adhesive layer (D) without absorbing moisture, the film was aged under vacuum at 50°C for 3 days, yielding a multilayer film 1 (12 in Figure 1) with the layer structure shown in Figure 1.

[0082] <Example 2> A substrate layer (A1) having an inorganic barrier layer (a2) was prepared under the same conditions as in Example 1, except that the high-frequency output of the film-forming conditions shown in Example 1 was changed to 300 W. The obtained substrate layer (A1) (A1 in FIG. 2) was measured in an atmosphere of 40°C and 90% RH. Moisture permeability But 8 x 10 -4 g / m 2 Instead of the coating film (i) shown in Example 1, a coating film (ii) (21 in Figure 2) was used, in which the coating liquid A was applied by a bar coater onto the inorganic barrier layer (a2) on the side opposite the PET of the base layer (A1), and a multilayer film 2 (22 in Figure 2) was obtained in the same manner as in Example 1.

[0083] Example 3 A biaxially stretched PET film having a thickness of 100 μm was used for the plastic layer (x), and an inorganic barrier layer (a1) of silicon oxide was formed on both sides of the film using a plasma CVD apparatus under the film-forming conditions of Example 1, and an inorganic barrier layer (a2) of silicon oxide was formed under the film-forming conditions of Example 2, to obtain a substrate layer (A1). The obtained substrate layer (A1) (A1 in FIG. 3) was measured in an atmosphere of 40°C and 90% RH. Moisture permeability But 9 x 10 -5 g / m 2 Using a coating film (iii) (31 in Fig. 3) in which a moisture-trapping layer (B1) was formed by applying coating liquid A onto an inorganic barrier layer (a2) with a bar coater, a 12 µm-thick PET film was dry-laminated onto the moisture-trapping layer (B1) (B1 in Fig. 3) as a plastic layer (C) via an adhesive layer (D) in the same manner as in Example 1 to obtain a multilayer film 3 (32 in Fig. 3).

[0084] Example 4 In Example 1, instead of the 12 μm thick PET film used for the plastic layer (C), a 40 ℃9 Under 0%RH atmosphere Moisture permeability is 0.15g / m 2 The inorganic barrier layer (a4) side of a commercially available barrier film (Techbarrier LS, manufactured by Mitsubishi Chemical) having a coating film (i) of 1000 ppm / day was (41 in Figure 4) A multilayer film 4 (42 in FIG. 4) was obtained in the same manner as in Example 1, except that the above-mentioned film was dry-laminated onto the moisture-trapping layer (B1).

[0085] <Example 5> Two substrate layers (A1) obtained in Example 1 were used, and one of them was used as the inorganic barrier layer (a1) side, instead of the 12 μm thick PET film used in the plastic layer (C) in Example 1. adhesive layer (D) through the coating film (i) (51 in Figure 5) A multilayer film 5 (52 in FIG. 5) was obtained in the same manner as in Example 1, except that the above-mentioned film was dry-laminated onto the moisture-trapping layer (B1).

[0086] <Comparative Example 1> The substrate layer (A1) (A1 in FIG. 6) was prepared under the same conditions as in Example 1, except that the high-frequency output of the film-forming conditions shown in Example 1 was changed to 300 W. Moisture permeability is 2.1×10 -3 g / m 2 A multilayer film 6 (62 in FIG. 6) was obtained in the same manner as in Example 1, except that the temperature was changed to / day.

[0087] <Evaluation test> The laminated specimens prepared above were heated at 40°C and 90%RH using the method described above. RH Under the atmosphere Moisture permeability The results are shown in Table 1. In Examples 1 to 5, unlike Comparative Example 1, the multilayer film was heated at 40°C and 90% RH. Moisture permeability is 1 x 10 -6 g / m 2 / day.

[0088] [Table 1] [Explanation of symbols]

[0089] 11 Coating film (i) 12 Gas barrier multilayer film 1 21 Coating film (ii) 22 Gas barrier multilayer film 2 31 Coating film (iii) 32 Gas barrier multilayer film 3 41 Coating film (iv) 42 Gas barrier multilayer film 4 51 Coating film (v) 52 Gas barrier multilayer film 5 61 Coating film (vi) 62 Gas barrier multilayer film 6 A1 Base material layer A2 base material layer x Plastic layer y plastic layer a1 Inorganic barrier layer a2 inorganic barrier layer a4 inorganic barrier layer B1 Moisture trapping layer C Plastic layer D Adhesive layer

Claims

1. The sheet comprises a substrate layer (A1), a moisture-trapping layer (B1), and an outer layer (Q) in this order, the substrate layer (A1) has a layer selected from the group consisting of an inorganic barrier layer (a1) and an inorganic barrier layer (a2) on at least one surface of the plastic layer (x), the outer layer (Q) has a layer selected from the group consisting of a plastic layer (C), the substrate layer (A1) and the substrate layer (A2), The base layer (A2) is a layer having an inorganic barrier layer (a4) on one surface of a plastic layer (y), the moisture permeability (40°C, RH 90%) of the substrate layer (A1) is 2.0 × 10 -4 g / m 2 / day or less; The layer structure is as follows: Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a3) / plastic layer (C), inorganic barrier layer (a1) / plastic layer (x) / moisture-trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a1) / plastic layer (x), Inorganic barrier layer (a1) / plastic layer (x) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a4) / plastic layer (y), Plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / plastic layer (C), Inorganic barrier layer (a1) / plastic layer (x) / inorganic barrier layer (a2) / moisture trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a3) / plastic layer (C), inorganic barrier layer (a1) / plastic layer (x) / inorganic barrier layer (a2) / moisture-trapping layer (B1) / adhesive layer (D) / inorganic barrier layer (a1) / plastic layer (x), Either Gas barrier multilayer film.

2. 2. The gas barrier multilayer film according to claim 1, wherein the inorganic barrier layers (a1) to (a4) are metal oxide films.

3. 3. The gas barrier multilayer film according to claim 1, wherein the plastic layers (x) to (y) contain an olefin resin, a polyester resin, a polyimide resin, a polyamide resin, or a cyclic olefin resin.

4. 3. The gas barrier multilayer film according to claim 1, wherein the moisture-trapping layer (B1) contains a resin composition in which a moisture absorbent (ii) is dispersed in an ionic polymer (i).

5. 3. The gas barrier multilayer film according to claim 1, wherein the plastic layer (C) contains an olefin resin, a polyester resin, a polyimide resin, a polyamide resin, or a cyclic olefin resin.

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