JP6645137B2 - Gas barrier pressure-sensitive adhesive sheet and electronic device having the same - Google Patents

Description

  The present invention relates to a gas barrier pressure-sensitive adhesive sheet and an electronic device including the same. More specifically, the present invention has a small thickness, can easily impart gas barrier properties to an adherend, and does not peel off at the pressure-sensitive adhesive layer interface even under high temperature and high humidity conditions, and The present invention relates to a gas-barrier pressure-sensitive adhesive sheet excellent in point pressure resistance and an electronic device including the same.

  Conventionally, in the fields of food, packaging materials, pharmaceuticals, etc., in order to prevent gas such as water vapor and oxygen from permeating, a relatively simple inorganic film such as a metal or metal oxide deposited film is provided on the surface of a resin base material. A gas barrier film having a structure (hereinafter, referred to as a gas barrier film in the present application) has been used.

  In recent years, such gas barrier films that prevent the permeation of water vapor, oxygen, and the like are being used in the field of electronic devices such as liquid crystal display devices (LCD), solar cells (PV), and organic electroluminescence (EL) devices. . In order to provide such an electronic device with flexibility, lightness, and resistance to breakage, a gas barrier film having high gas barrier properties is required instead of a hard and easily breakable glass substrate.

  As a measure for obtaining a gas barrier film applicable to an electronic device, for example, in Patent Document 1, a transparent gas composed of a metal oxide is formed on a transparent plastic film surface by an evaporation method, an ion plating method, a sputtering method, or the like. A flexible display substrate on which a barrier layer is laminated is disclosed.

  However, the flexible display substrate described in Patent Literature 1 has a problem in that excessive heat is applied to the plastic base material, which adversely affects the optical characteristics of the plastic base material and lowers the transparency.

  As a method for solving this, a method using a transfer laminate having a gas barrier layer can be considered. For example, Patent Document 2 discloses that after forming a hard coat layer on a heat-resistant support, a gas barrier layer is formed on the hard coat layer to obtain a transfer laminate, and then a base made of a polymer material is used. The material and the gas barrier layer of the transfer laminate are bonded via an adhesive, and then the heat-resistant support is peeled off to form a gas barrier layer on the substrate made of a polymer material. A method for obtaining a plastic substrate for a liquid crystal display element on which a coat layer is laminated is described.

  Patent Document 3 discloses a transfer foil for a plastic liquid crystal panel in which at least one hard coat layer, a gas barrier layer, and an adhesive layer are sequentially formed on a base film directly or via a release layer. Patent Document 3 also discloses a method of manufacturing a plastic liquid crystal panel by transferring the transfer foil to a plastic substrate by a thermal transfer method.

In the transfer laminates described in Patent Literatures 2 and 3, when the transfer laminate is rolled or bent, the gas barrier layer and the adhesive layer are peeled off, and blisters and floats are formed between these layers. May occur. In addition, when the transfer laminate is adhered to an adherend such as a plastic substrate and placed under high temperature and high humidity conditions, the interface between the adhesive layer and the adherend floats, and the transfer laminate However, there is a problem that it is easily peeled off from the adherend. Therefore, as a solution to such a problem, Patent Document 4 discloses a gas-barrier pressure-sensitive adhesive sheet having at least one gas barrier layer and at least one pressure-sensitive adhesive layer, and the storage elastic modulus of the pressure-sensitive adhesive layer at 23 ° C. Is in the range of 1.5 × 10 ^{4 to} 1.0 × 10 ⁷ Pa and has no base material layer, and a gas barrier pressure-sensitive adhesive sheet is disclosed.

  However, the present inventors have studied that the gas barrier pressure-sensitive adhesive sheet does not have a base material layer, so that the gas barrier layer is easily degraded by the point pressure, and the gas barrier property itself is easily degraded with it. It turned out that there was a problem.

JP 2000-338901 A JP-A-8-179291 JP-A-8-234181 WO 2013/018602

  The present invention has been made in view of the above-described problems and circumstances, and the problem to be solved is that the thickness is small, a gas barrier property can be easily imparted to an adherend, and high temperature and high humidity conditions An object of the present invention is to provide a gas-barrier pressure-sensitive adhesive sheet which does not peel off at the pressure-sensitive adhesive layer interface and has excellent point pressure resistance, and an electronic device including the same.

In order to solve the above-mentioned problems, the present inventor, in the course of examining the cause of the above-mentioned problems, places a non-transition metal M1 (silicon (Si 2 )) and a transition metal M2 (niobium (Nb) or tantalum The present inventors have found that the above problem can be solved by providing a gas barrier layer having a mixed region containing (Ta)), and have reached the present invention.

  That is, the above object according to the present invention is solved by the following means.

1. A gas barrier pressure-sensitive adhesive sheet having a gas barrier layer and a pressure-sensitive adhesive layer on a substrate,
In the gas barrier layer, at least in the thickness direction, a mixed region containing a non-transition metal M1 (silicon (Si 2 )) and a transition metal M2 (niobium (Nb) or tantalum (Ta)) is continuously formed in the thickness direction. A gas barrier property having at least 5 nm and wherein the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the mixed region satisfies the following relational expression (2): Adhesive sheet.
Chemical composition formula _{(1) :( M1) (M2} ) x O y N z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Wherein, M1: non-transition metal (silicon (Si 2 )) , M2: transition metal (niobium (Nb) or tantalum (Ta)), O: oxygen, N: nitrogen, x, y, z: stoichiometry Coefficient, a: maximum valence of M1, b: maximum valence of M2. The expression on the left side of relational expression (2) is an index of the degree of oxygen deficiency.)

  2. The gas barrier layer is provided between the region A which is a region containing the transition metal M2 as the main component of the metal and the region B which is a region containing the non-transition metal M1 as the main component of the metal. 2. The gas-barrier pressure-sensitive adhesive sheet according to item 1, having a region.

3 . The gas barrier pressure-sensitive adhesive sheet according to any one of claims 1 to 2 , wherein the transition metal M2 is niobium (Nb).

4 . The size of the oxygen vacancies of the indices of the formula of the left side of the equation (2) is, from the first term, characterized in that in the range of 0.60 to 0.88 up to paragraph 3 The gas-barrier pressure-sensitive adhesive sheet according to any one of the preceding claims.

5 . An electronic device comprising the gas-barrier pressure-sensitive adhesive sheet according to any one of items 1 to 4 .

6 . The electronic device according to claim 5 , comprising an organic electroluminescence element.

  By the above means of the present invention, the thickness is small, the gas barrier property can be easily imparted to the adherend, and even under high temperature and high humidity conditions, it does not peel off at the interface of the pressure-sensitive adhesive layer, and It is possible to provide a gas-barrier pressure-sensitive adhesive sheet having excellent pressure resistance and an electronic device including the same.

  Although the mechanism of manifesting or acting the effects of the present invention has not been clarified, it is speculated as follows.

  The present inventors formed a layer containing a transition metal in contact with an inorganic precursor layer containing a non-transition metal as a main component, thereby forming an inorganic precursor layer containing a non-transition metal as a main component and a transition metal-containing layer. A new gas barrier layer using a novel gas barrier property development mechanism, in which a mixed region where non-transition metal and transition metal interdiffuse is formed at the interface with the layer, and this mixed region develops gas barrier properties The composition was found. And it came to find that this new gas barrier layer has little deterioration with respect to a point-like pressing pressure.

  This mixed region has a gradient composition in which the mixing ratio of the non-transition metal and the transition metal changes continuously, and has a thickness of about 30 nm as an example.

  It is considered that the physical properties of this mixed region are also continuously changing in accordance with such a gradient composition in which the composition ratio changes continuously. Further, it is considered that the gas barrier property is continuously changed, such that the gas barrier property is highest at the center of the mixed region, and the gas barrier property is lower as going to the surface layer side or the base material side. . It is considered that, due to such physical properties that continuously change in the thickness direction, cracks are unlikely to occur in the gas barrier layer even when subjected to deformation due to a point-like pressing force.

Sectional drawing which shows the example of the gas-barrier adhesive sheet of this invention. Conceptual diagram showing composition distribution state of non-transition metal and transition metal in thickness direction of gas barrier layer FIG. 2 is a cross-sectional view illustrating a configuration of an organic EL element according to an embodiment of the electronic device of the present invention.

The gas-barrier pressure-sensitive adhesive sheet of the present invention is a gas-barrier pressure-sensitive adhesive sheet having a gas barrier layer and a pressure-sensitive adhesive layer on a substrate, wherein the gas barrier layer has a non-transition metal M1 (at least in a thickness direction). silicon a mixed region containing (Si)) and the transition metal M2 (niobium (Nb) or tantalum (Ta)), have more than 5nm continuously in the thickness direction, and the composition of the mixed area, the chemical When represented by the composition formula (1), at least a part of the mixed region satisfies the relational expression (2). This feature is a technical feature common to or corresponding to each of the following embodiments.

  As an embodiment of the present invention, it is preferable that the gas barrier layer has the mixed region between the A region and the B region from the viewpoint of achieving the effects of the present invention.

Further, it is preferable that the non-transition metal M1 is silicon (Si) from the viewpoint of gas barrier properties. Furthermore, before Symbol transition metal M2 is, it is preferable from the same viewpoint is niobium (Nb).

Further, from the same viewpoint, it is preferable that the composition of the mixed region has a non-stoichiometric composition in which oxygen is deficient, which will be described later. That is, it is preferable that the magnitude of the oxygen deficiency index represented by the expression on the left side of the relational expression (2) is in the range of 0.60 to 0.88.

  The gas barrier pressure-sensitive adhesive sheet of the present invention can be suitably used for various electronic devices, for example, an electronic device having a quantum dot-containing resin layer and an organic electroluminescence element.

Hereinafter, the present invention, its components, and embodiments and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit.
<< Outline of Gas Barrier Adhesive Sheet of the Present Invention >>
The gas barrier pressure-sensitive adhesive sheet of the present invention is a gas barrier pressure-sensitive adhesive sheet having a gas barrier layer and a pressure-sensitive adhesive layer on a substrate,
In the gas barrier layer, a mixed region containing a non-transition metal M1 (silicon (Si 2 )) and a transition metal M2 (niobium (Nb) or tantalum (Ta)) is continuous in the thickness direction at least in the thickness direction. A gas barrier characterized in that, when the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the mixed region satisfies the following relational expression (2): Adhesive sheet.
Chemical composition formula _{(1): (M1) (} M2) x O y N z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Wherein, M1: non-transition metal (silicon (Si 2 )) , M2: transition metal (niobium (Nb) or tantalum (Ta)), O: oxygen, N: nitrogen, x, y, z: stoichiometry Coefficient, a: maximum valence of M1, b: maximum valence of M2. The expression on the left side of relational expression (2) is an index indicating the degree of oxygen deficiency.)
According to an embodiment of the present invention, the gas barrier layer is provided between an A region containing the transition metal M2 as a main component of the metal and a B region containing the non-transition metal M1 as a main component of the metal. It is preferable that the embodiment has the mixed region. The mixed region may be a region where at least a part thereof overlaps the A region or the B region.

The gas barrier properties of the gas barrier layer according to the present invention, when calculated on a laminate in which the gas barrier layer is formed on a substrate, the oxygen permeability measured by a method in accordance with JIS K 7126-1987, ^{1 × 10 -3 cm 3 / (} m 2 · 24h · atm) or less, which is measured by the method based on JIS K 7129-1992, the water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2) % RH) is preferably a ^{1 × 10 -3 g / (m} 2 · 24h) or less of the high gas barrier properties.

<< Configuration of Gas Barrier Adhesive Sheet of the Present Invention >>
As long as the gas barrier pressure-sensitive adhesive sheet of the present invention satisfies the above conditions, the order of lamination and the number of layers are not particularly limited, and only one surface may be a pressure-sensitive adhesive layer surface as shown in FIG. As shown in FIG. 1B, both surfaces may be pressure-sensitive adhesive layer surfaces, or may have a protective layer as shown in FIG. 1C. Further, as shown in FIG. 1D, two or more gas barrier layers and protective layers may be provided.

  Among these gas-barrier pressure-sensitive adhesive sheets, those having two or more gas barrier layers are preferable because of their excellent gas-barrier properties.

The gas barrier pressure-sensitive adhesive sheet S1 shown in FIG. 1A includes a substrate 1, a gas barrier layer 2, an adhesive layer 3 adjacent to the gas barrier layer 2, and a peeling adjacent to the outer surface of the adhesive layer 3. It comprises a sheet 4a and a release sheet 4b adjacent to the outer surface of the substrate 1.
The gas-barrier pressure-sensitive adhesive sheet S2 shown in FIG. 1B has a laminate in which a pressure-sensitive adhesive layer 3a, a substrate 1, a gas barrier layer 2, and a pressure-sensitive adhesive layer 3b are laminated in this order, and an outer surface of the pressure-sensitive adhesive layer 3a. It consists of an adjacent release sheet 4a and a release sheet 4b adjacent to the outer surface of the pressure-sensitive adhesive layer 3b.
The gas barrier pressure-sensitive adhesive sheet S3 shown in FIG. 1C is adjacent to a laminate in which a pressure-sensitive adhesive layer 3a, a substrate 1, a gas barrier layer 2, and a protective layer 5 are laminated in this order, and an outer surface of the pressure-sensitive adhesive layer 3a. And a release sheet 4b adjacent to the outer surface of the protective layer 5.
The gas barrier pressure-sensitive adhesive sheet S4 shown in FIG. 1D includes a pressure-sensitive adhesive layer 3a, a protective layer 5a, a gas barrier layer 2a, a pressure-sensitive adhesive layer 3b, a protective layer 5b, a substrate 1, a gas barrier layer 2b, and a pressure-sensitive adhesive layer. 3c, a release sheet 4a adjacent to the outer surface of the pressure-sensitive adhesive layer 3a, and a release sheet 4b adjacent to the outer surface of the pressure-sensitive adhesive layer 3c.

  Examples of the gas barrier pressure-sensitive adhesive sheet containing a conductor layer and a protective layer include (conductor layer / substrate / gas barrier layer / pressure-sensitive adhesive layer), (conductor layer / protective layer / substrate / gas barrier layer / (Pressure-sensitive adhesive layer), (pressure-sensitive adhesive layer / protective layer / substrate / gas barrier layer / pressure-sensitive adhesive layer), (pressure-sensitive adhesive layer / substrate / gas barrier layer / pressure-sensitive adhesive layer / gas barrier layer / pressure-sensitive adhesive layer), (Protective layer / substrate / gas barrier layer / adhesive layer / substrate / gas barrier layer / adhesive layer), (protective layer / substrate / gas barrier layer / adhesive layer / protective layer / gas barrier layer / adhesive) That have a layer configuration such as an agent layer).

  In addition, the said structure represents the structure at the time of use (excluding the release sheet).

  The gas-barrier pressure-sensitive adhesive sheet of the present invention applies point-like pressure, bends, and peels off at the interface between the pressure-sensitive adhesive layer and other layers even after being placed under high temperature and high humidity for a long time. It is hard to cause blistering and floating, and has excellent point pressure resistance, bending resistance, heat resistance and moisture resistance.

Since the gas barrier pressure-sensitive adhesive sheet of the present invention is lightweight and has excellent gas barrier properties, an electronic member, an optical member, a packaging material for foods and beverages and pharmaceuticals and the like are adhered as an adherend via a pressure-sensitive adhesive layer. This makes it possible to easily impart various performances such as gas barrier properties to the adherend without impairing the appearance of the adherend. Therefore, the gas-barrier pressure-sensitive adhesive sheet of the present invention can be used as a gas-barrier pressure-sensitive adhesive sheet for electronic members, optical members, and packaging materials for foods and drinks and pharmaceuticals. Above all, it is preferably used as an electronic member or an optical member, and in particular, an electronic member such as a flexible display substrate or the like that requires flexibility and a plastic substrate for a liquid crystal display element or the like that requires heat resistance and moisture resistance. It is preferably used for
<< Each component of gas barrier film >>
Hereinafter, the substrate, the gas barrier layer, and the like constituting the gas barrier film of the present invention will be described in detail.
[Base material]
Examples of the substrate used in the present invention include a film or sheet made of a colorless and transparent resin. Examples of the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP) and cyclopolyolefin; polyamides Polycarbonate resins; Polyvinyl alcohol resins; Saponified ethylene-vinyl acetate copolymers; Polyacrylonitrile resins; Acetal resins; Polyimide resins; Cellulose ester resins.

  Among these resins, a resin selected from a polyester resin, a polyimide resin, a cyclopolyolefin resin, and a polycarbonate resin is particularly preferable. These resins may be used alone or in combination of two or more.

  The thickness of the substrate can be appropriately set in consideration of the stability at the time of producing the gas barrier film of the present invention. The thickness of the substrate is preferably in the range of 5 to 500 μm from the viewpoint that the film can be transported even in vacuum.

  Furthermore, when forming the gas barrier layer according to the present invention by the plasma CVD method, the thickness of the base material is in the range of 50 to 200 μm because the gas barrier layer is formed while discharging through the base material. More preferably, it is particularly preferably in the range of 50 to 100 μm.

Further, it is preferable that the base material is subjected to a surface activation treatment for cleaning the surface of the base material from the viewpoint of adhesion to a gas barrier layer described later. Examples of such a surface activation treatment include a corona treatment, a plasma treatment, and a flame treatment.
[Gas barrier layer]
The gas barrier layer according to the present invention has a mixed region containing a non-transition metal M1 (silicon (Si 2 )) and a transition metal M2 (niobium (Nb) or tantalum (Ta)) at least in the thickness direction. A gas barrier layer having a thickness of 5 nm or more continuously in the vertical direction.

Further, as the gas barrier layer, the region A containing the transition metal M2 (niobium (Nb) or tantalum (Ta)) as the main component a of the metal, and the non-transition metal M1 (silicon (Si 2 )) In a preferred embodiment, the mixed region containing a compound derived from the main component a and the main component b is provided between the region B contained as the component b and the compound B.

  Further, in a preferred embodiment, the gas barrier layer according to the present invention has a configuration in which the mixed region is formed over the entire region in the layer.

In this mixing area, it is preferable that the said transition metal M2 non-transition metal M1, and oxygen is contained. Further, the mixed area, a mixture of oxides of the oxide and the non-transition metal M1 of the transition metal M2, or at least one of composite oxide of the transition metal M2 and the non-transition metal M1 is contained it is is a preferred form, it is more preferred form the composite oxide of the transition metal M2 and the non-transition metal M1 is contained.

  In addition, when the composition of the mixed region is represented by the following chemical composition formula (1), it is preferable that at least a part of the mixed region satisfies the condition defined by the following relational expression (2).

Chemical composition formula _{(1) :( M1) (M2} ) x O y N z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
In the above formulas, M1 represents a non-transition metal (silicon (Si 2 )) , M2 represents a transition metal (niobium (Nb) or tantalum (Ta)), O represents oxygen, and N represents nitrogen. x, y, and z are stoichiometric coefficients, respectively, and a represents the maximum valence of M1 and b represents the maximum valence of M2.

Hereinafter, the details of the gas barrier layer according to the present invention will be further described.
(Each region constituting gas barrier layer)
The region constituting the gas barrier layer according to the present invention will be described, and the definition of technical terms used below will be described in advance.

  In the present invention, the “region” refers to a plane that is substantially perpendicular to the thickness direction of the gas barrier layer (that is, a plane that is parallel to the outermost surface of the gas barrier layer) and has a constant or arbitrary thickness. Refers to a three-dimensional range (region) between two opposing surfaces formed when divided in. The composition of components in the region gradually changes even if it is constant in the thickness direction. You may do.

  The “component” in the present invention refers to a compound constituting a specific region of the gas barrier layer and a simple substance of a metal or a nonmetal. Further, the “main component” in the present invention refers to a component having the largest content as an atomic composition ratio. For example, a “main component of a metal” refers to a metal component having the largest atomic composition ratio among the metal components in the constituent components.

  The “mixture” in the present invention refers to a state in which the components of the regions A and B are mixed without being chemically bonded to each other. For example, a state in which niobium oxide and silicon oxide are mixed without being chemically bonded to each other.

  The “compound derived from the main component a and the main component b” in the present invention refers to the main component a and the main component b themselves, and a composite compound formed by the reaction of the main component a and the main component b.

  Explaining a “composite oxide” as a specific example of the composite compound, the “composite oxide” is a compound (oxide) formed by the components of the regions A and B being chemically bonded to each other. Say. For example, it refers to a compound having a chemical structure in which a niobium atom and a silicon atom form a chemical bond directly or via an oxygen atom.

  In the present invention, a complex in which the components of the regions A and B are physically bonded to each other by intermolecular interaction is also included in the “composite oxide” according to the present invention. And

Next, each region will be described in detail.
(Transition metal (niobium (Nb) or tantalum (Ta)) containing region: A region)
Wherein the transition metal-containing region in which A region means a region containing the transition metal as a main component a metal. The term "the compound", i.e. a "compound of the transition metal" refers to a compound containing the transition metal, for example, it refers to the transition metal oxide.

The transition metal (M2), niobium (Nb) or tantalum (Ta) may be used alone or in combination.

In particular, the a transition metal (M2) is Nb, the detail is a non-transition metal (M1) is Si described later, it is possible to obtain the effect of improving the significant gas barrier properties, a particularly preferred combination. It is considered that this is because the bond between Si and Nb is particularly likely to occur .

The thickness of the region A is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, and more preferably in the range of 5 to 15 nm, from the viewpoint of achieving both gas barrier properties and optical characteristics. It is more preferred that there be.
(Non-transition metal (silicon (Si 2 ))- containing region: B region)
The region B as the non-transition metal-containing region refers to a region containing the non-transition metal as a main component b as a metal. The “compound” or “compound of the non-transition metal” as used herein refers to a compound containing the non-transition metal, for example, the non-transition metal oxide.

As the non-transition metal, (silicon (Si 2 )) can be used alone or in combination. Among them, Si alone is particularly preferable.

The thickness of the B region is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm, and more preferably in the range of 50 to 300 nm, from the viewpoint of achieving both gas barrier properties and productivity. It is more preferred that there be.
(Mixed area)
The mixed region according to the present invention is a mixed region containing a non-transition metal (M1: silicon (Si 2 )) and a transition metal (M2: niobium (Nb) or tantalum (Ta)). It is a region having 5 nm or more continuously.

  Here, the mixed region may be formed as a plurality of regions where the chemical compositions of the components are different from each other, or may be formed as a region where the chemical composition of the components is continuously changing. .

The region other than the mixing zone of the gas barrier layer, said oxide of a non-transition metals (M1), a nitride, oxynitride, may be a region such as an acid carbide, the transition metal (M2) The region may be an oxide, a nitride, an oxynitride, an oxycarbide, or the like.
(Oxygen deficiency composition)
In the present invention, it is preferable that a part of the composition contained in the mixed region according to the present invention is a non-stoichiometric composition in which oxygen is deficient (oxygen deficiency composition).

In the present invention, when the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the composition of the mixed region is defined by the following relational expression (2). It is defined as meeting the conditions. As the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the certain mixed region is used. Details will be described later.
Chemical composition formula (1)
(M1) (M2) _x O _y N _z
Relational expression (2)
(2y + 3z) / (a + bx) <1.0
In the above formulas, non-transition metal M1 (silicon (Si)), M2 is a transition metal (niobium (Nb) or tantalum (Ta)), O is oxygen, N represents represents nitrogen, x, y and z are each Represents the stoichiometric coefficient. a represents the maximum valence of M1 and b represents the maximum valence of M2.

  Hereinafter, when no special distinction is necessary, the composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.

As described above, the composition of the composite region between the non-transition metals according to the present invention (M1) and the transition metal (M2) is an expression (1) _{(M1) (M2)} represented by _x O y _{N z} It is. As is clear from this composition, the composition of the composite region may partially include a nitride structure, and preferably includes a nitride structure from the viewpoint of barrier properties.

Here, the maximum valence of non-transition metal (M1) a, the maximum valence of b, and valence of O 2, N valence of 3 of the transition metal (M2). Then, when the composition of the composite region (including a part that is partially nitrided) has a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This equation means that the the sum of the bonds of non-transition metals (M1) and the transition metal (M2), O, and the sum of the bonds of N are equal, in this case, the non-transition metals (M1) and the transition metal (M2) both, so that is bonded to one of O and N. In the present invention, the or if two or more as the non-transition metal (M1) is used in combination, when said two or more transition metal (M2) is used together, the maximum valence of each element each Compound valences calculated by weighted averaging based on the abundance ratios of the elements are adopted as the values of a and b of the respective “maximum valences”.

On the other hand, in the mixed area according to the present invention, when the (2y + 3z) / (a + bx) <1.0 indicated by the equation (2), the binding of the non-transition metal (M1) and the transition metal (M2) This means that the total number of O and N bonds is insufficient with respect to the total number of hands, and such a state is the above-described “oxygen deficiency”.

Oxygen in the deficient state, the excess bonds of non-transition metals (M1) and the transition metal (M2) has the potential to bind to each other, the non-transition metal (M1) and the transition metal (M2 It is considered that, when the metals are directly bonded to each other, a denser and denser structure is formed than when the metals are bonded via O and N, and as a result, the gas barrier property is improved.

In the present invention, the mixed region is a region where the value of x satisfies 0.02 ≦ x ≦ 49 (0 <y, 0 ≦ z). This is the value of the atomic ratio of the transition metal (M2) / the non-transition metal (M1) is in the range of from 0.02 to 49, is defined as the thickness is 5nm or more regions, and the This is the same definition.

In this region, there since the both non-transition metal (M1) and the transition metal (M2) is directly involved in binding between metals, satisfies this condition mixed region with a thickness greater than a predetermined value (5 nm) This is considered to contribute to the improvement of gas barrier properties. Note that the since the existence ratio of non-transition metals (M1) and the transition metal (M2) is considered can contribute more to the improvement of gas barrier properties close, mixing region satisfies 0.1 ≦ x ≦ 10 The region preferably has a thickness of 5 nm or more, more preferably a region satisfying 0.2 ≦ x ≦ 5 has a thickness of 5 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 has a thickness of 5 nm or more. More preferably, it is included in the thickness.

  Here, as described above, if there is a region that satisfies the relationship of (2y + 3z) / (a + bx) <1.0 represented by the relational expression (2) within the range of the mixed region, the effect of improving the gas barrier property is improved. Although it has been confirmed that the mixed region is exhibited, at least a part of the composition of the mixed region preferably satisfies (2y + 3z) / (a + bx) ≦ 0.9, and (2y + 3z) / (a + bx) ≦ 0.85. More preferably, it satisfies (2y + 3z) / (a + bx) ≦ 0.8. Here, as the value of (2y + 3z) / (a + bx) in the mixed region decreases, the effect of improving gas barrier properties increases, but absorption of visible light also increases. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, it is preferable that 0.2 ≦ (2y + 3z) / (a + bx), and that 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and it is still more preferable that 0.4 ≦ (2y + 3z) / (a + bx).

In the present invention, the thickness of the mixed region where a good gas barrier property is obtained is 5 nm or more as a sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and the thickness is 8 nm or more. Is preferably 10 nm or more, and more preferably 20 nm or more. The thickness of the mixed region has no particular upper limit from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.

  The gas barrier layer having the mixed region having the specific configuration as described above exhibits, for example, a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.

(Composition analysis by XPS and measurement of thickness of mixed region)
The composition distribution in the mixed region, the A region, and the B region of the gas barrier layer according to the present invention, the thickness of each region, and the like are described in detail below using X-ray Photoelectron Spectroscopy (abbreviation: XPS). It can be determined by measuring with.

Hereinafter, a method of measuring the mixed region, the A region, and the B region by the XPS analysis method will be described.
The element concentration distribution curve (hereinafter, referred to as “depth profile”) in the thickness direction of the gas barrier layer according to the present invention is, specifically, the element concentration of the non-transition metal M1 (for example, silicon), the transition metal M2 ( For example, the element concentration of niobium), oxygen (O), nitrogen (N), and carbon (C) element concentration can be measured by using X-ray photoelectron spectroscopy and rare gas ion sputtering such as argon together. The barrier layer can be formed by sequentially performing surface composition analysis while exposing the inside from the surface.

The distribution curve obtained by such XPS depth profile measurement can be created, for example, by setting the vertical axis to the atomic ratio (unit: atom%) of each element and the horizontal axis to the etching time (sputtering time). In this manner, in the distribution curve of the elements having the etching time on the horizontal axis, since the etching time is substantially correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in XPS depth profile measurement is used. Can be adopted. In addition, as a sputtering method employed in measuring the XPS depth profile, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm /. It is preferably set to be sec (equivalent value of thermal oxide film of SiO ₂ ).

Hereinafter, an example of specific conditions of the XPS analysis applicable to the composition analysis of the gas barrier layer according to the present invention will be described.
・ Analyzer: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: monochromatic Al-Kα
・ Sputter ion: Ar (2 keV)
Depth profiles: in terms of SiO ₂ sputter thickness, repeat the measurement at a predetermined thickness intervals, determination of the depth depth profile. The thickness interval was 1 nm (data at every 1 nm in the depth direction is obtained).
-Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak areas. For data processing, MultiPak manufactured by ULVAC-PHI is used. The analyzed elements are non-transition metal M1 (for example, silicon (Si)), transition metal M2 (for example, niobium (Nb)) , oxygen (O), nitrogen (N), and carbon (C).

From the data obtained, the composition ratio calculated, wherein said transition metal and the non-transition metal (M1) (M2) coexist, and the number of atoms of transition metal (M2) / the non-transition metal (M1) A range in which the value of the ratio is 0.02 to 49 is determined, this is defined as a mixed region, and the thickness thereof is determined. The thickness of the mixed region is obtained by expressing the sputtering depth in XPS analysis in terms of SiO ₂ .

  In the present invention, when the thickness of the mixed region is 5 nm or more, it is determined to be “mixed region”. From the viewpoint of gas barrier properties, there is no upper limit of the thickness in the mixed region, but from the viewpoint of optical characteristics, it is preferably in the range of 5 to 100 nm, more preferably in the range of 8 to 50 nm, and furthermore Preferably, it is in the range of 10 to 30 nm.

  Hereinafter, specific examples of the mixed region in the gas barrier layer according to the present invention will be described with reference to the drawings.

FIG. 2 is a graph for explaining an element profile and a mixed region when the composition distribution of the non-transition metal and the transition metal in the thickness direction of the gas barrier layer is analyzed by the XPS method. In FIG. F, the element analysis of the non-transition metal (M1), the transition metal (M2), O, N, and C is performed in the depth direction from the surface of the gas barrier layer (the left end of the graph). 5 is a graph showing the depth of sputtering (layer thickness: nm) and the vertical axis showing the content (atom%) of the non-transition metal (M1) and the transition metal (M2). From the right side, a region B having an elemental composition mainly containing the non-transition metal (M1, for example, Si) as a metal is shown, and the transition metal (M2, for example, niobium) as a metal is contacted on the left side. Region A, which is an element composition as a main component, is shown. The mixed region is a region in which the value of the ratio of the number of atoms of the transition metal (M2) / the non-transition metal (M1) is represented by an elemental composition in a range of 0.02 to 49, and a part of the A region. This is a region that overlaps with a part of the B region and has a thickness of 5 nm or more.
[Method of forming each region]
(Transition metal (niobium (Nb) or tantalum (Ta)) containing region: formation of A region)
The transition metal (M2) according to the present invention includes Nb and Ta from the viewpoint of obtaining good gas barrier properties as described above. Nb and Ta are preferably used because they are considered to easily bond to the non-transition metal (M1: silicon (Si 2 )) contained in the gas barrier layer.

  The formation of the layer containing the oxide of the transition metal (M2) is not particularly limited. For example, a conventionally known vapor deposition method using an existing thin film deposition technique can be used to efficiently form a mixed region. It is preferable from the viewpoint of forming the film.

  These vapor phase film forming methods can be used by a known method. The vapor deposition method is not particularly limited. For example, a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, an ion assist vapor deposition method, a plasma CVD (chemical vapor deposition) method, and an ALD. (Atomic Layer Deposition) method and the like. Above all, it is preferable to form by a physical vapor deposition (PVD) method, since it is possible to form a film without damaging the functional element and to have high productivity, and it is more preferable to form by a sputtering method. preferable.

  The film formation by the sputtering method can be performed by one or a combination of two-pole sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like. The method of applying the target is appropriately selected according to the type of the target, and any of DC (direct current) sputtering, DC pulse sputtering, AC (alternating current) sputtering, and RF (high frequency) sputtering may be used.

  Further, a reactive sputtering method using a transition mode which is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable.

As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and it is preferable to use Ar. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, non-transition metals (M1: silicon (Si 2 )) and transition metals (M2: niobium (Nb) or tantalum (Ta)) can be obtained. A thin film of a composite oxide, a nitride oxide, an oxycarbide, or the like can be formed. The film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time and the like, and these can be appropriately selected according to a sputtering apparatus, a material of the film, a layer thickness, and the like.

Sputtering may be multiple simultaneous sputtering method using a plurality of sputtering targets, including the simple substance or oxide thereof of the transition metal (M2). For a method for producing these sputtering targets and a method for producing a thin film composed of a composite oxide using these sputtering targets, for example, JP-A-2000-160331, JP-A-2004-068109, The method and conditions described in JP 2013-047361 A can be appropriately referred to.

The film forming conditions for performing the co-evaporation method include a ratio of a transition metal (M2: niobium (Nb) or tantalum (Ta)) and oxygen in a film forming material, an inert gas and a reactive gas during film formation. And one or two or more conditions selected from the group consisting of the following ratios, the gas supply amount during film formation, the degree of vacuum during film formation, and the power during film formation. By adjusting the conditions (preferably, the oxygen partial pressure), a mixed region (C region) made of a composite oxide having an oxygen deficiency composition can be formed. That is, by forming the gas barrier layer using the above-described co-evaporation method, most of the region in the thickness direction of the formed gas barrier layer can be a mixed region. According to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixing region. In addition, in order to control the thickness of the mixed region, for example, the film formation time when performing the co-evaporation method may be adjusted.
(Non-transition metal (silicon (Si 2 ))- containing region: formation of B region)
In the gas barrier layer according to the present invention, the method for forming the B region containing the non-transition metal (M1) is not particularly limited, and for example, a vapor phase film forming method can be used by a known method. The vapor deposition method is not particularly limited. For example, a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, an ion assist vapor deposition method, a plasma CVD (chemical vapor deposition) method, and an ALD. (Atomic Layer Deposition) method and the like. Above all, it is preferable to form the film by physical vapor deposition (PVD) because the film can be formed without damaging the functional element and has high productivity. Can be formed as a target.

As another method, using a polysilazane-containing coating liquid containing Si as the non-transition metal, a method of forming by a wet coating method is also one of preferred methods.

In the present invention, “polysilazane” applicable to the formation of the B region is a polymer having a silicon-nitrogen bond in a structure, and is composed of SiO ₂ , Si _{3 made of} Si—N, Si—H, NH, or the like. N is ₄ and both of the intermediate solid solution _SiO x _N preceramic inorganic polymers, such as _y.
In order to form the B region constituting the gas barrier layer by using polysilazane so as not to impair the flatness of the above-described base material, a relatively low-temperature region as described in JP-A-8-112879 is used. Polysilazane which can be modified to silicon oxide, silicon nitride, or silicon oxynitride at a low temperature is preferable.

  Examples of such a polysilazane include compounds having a structure represented by the following general formula (1).

式中、Ｒ^１、Ｒ^２及びＲ^３は、各々水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルキルシリル基、アルキルアミノ基、又はアルコキシ基を表す。

In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

In the present invention, perhydropolysilazane (PHPS) in which all of R ¹ , R ^2, and R ³ are hydrogen atoms is particularly preferable from the viewpoint of the density of the B region constituting the obtained gas barrier layer as a thin film. .

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, whereby the adhesiveness to an adjacent base material is improved, and is hard and brittle. This is preferable in that the toughness can be imparted to the ceramic film made of polysilazane, and the occurrence of cracks can be suppressed even when the film thickness is increased.

These perhydropolysilazane and organopolysilazane may be appropriately selected depending on the use, and may be used as a mixture.
It is estimated that perhydropolysilazane has a structure in which a linear structure and a ring structure centered on a 6- or 8-membered ring coexist.

  Polysilazane has a number average molecular weight (Mn) of about 600 to 2,000 (polystyrene conversion), and is a liquid or solid substance, and varies depending on the molecular weight. These polysilazane compounds are commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane compound-containing coating solution.

  Other examples of polysilazane which can be ceramicized at a low temperature include silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with the above polysilazane (JP-A-5-238827), and glycidol-added polysilazane obtained by reacting glycidol (particularly, JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-299118). JP-A-6-306329), an acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (Japanese Patent Laid-Open No. 6-306329), and a metal-particle-added polysilazane obtained by adding metal fine particles (Japanese Patent Laid-Open No. 19698 JP), and the like.

In addition, for details of polysilazane, see, for example, paragraphs (0024) to (0040) of JP2013-255910A, paragraphs (0037) to (0043) of JP2013-188942A, and JP Paragraphs (0014) to (0021) of JP-A-2013-151123, paragraphs (0033) to (0045) of JP-A-2013-052569, and paragraphs (0062) to (0075) of JP-A-2013-129557. ), And the contents described in paragraphs (0037) to (0064) of JP-A-2013-226758 can be applied.
<Coating solution containing polysilazane>
As an organic solvent for preparing a coating solution containing polysilazane, it is preferable to avoid using an alcohol-based or water-containing solvent that easily reacts with polysilazane. Suitable organic solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and ethers such as alicyclic ethers. it can. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, Solvesso, and turbene; halogen hydrocarbons such as methylene chloride and trichloroethane; and ethers such as dibutyl ether, dioxane, and tetrahydrofuran. These organic solvents may be selected according to the purpose, such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed. The concentration of polysilazane in the coating solution containing polysilazane varies depending on the intended thickness of the gas barrier layer and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass.

  Further, an amine or metal catalyst may be added to the coating solution containing polysilazane in order to promote the modification to silicon oxide, silicon nitride, or silicon oxynitride. For example, a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to. In addition, these commercially available products may be used alone or in combination of two or more. In the polysilazane-containing coating solution, the amount of the catalyst is adjusted to 2% by mass or less based on the polysilazane in order to avoid excessive formation of silanol by the catalyst, decrease in film density, increase in film defects, and the like. Is preferred.

  The coating solution containing polysilazane may contain an inorganic precursor compound in addition to polysilazane. The inorganic precursor compound other than polysilazane is not particularly limited as long as a coating solution can be prepared. For example, compounds other than polysilazane described in paragraphs “0110” to “0114” of JP-A-2011-143577 can be appropriately employed.

(Additive element)
An organometallic compound of a metal element other than Si can be added to the coating solution containing polysilazane. By adding an organometallic compound of a metal element other than Si, in the coating and drying process, replacement of N and O atoms of polysilazane is promoted, and after coating and drying, the composition can be changed to a stable composition close to SiO _2. it can.

  Examples of metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl) and the like.

  Particularly, Al, B, Ti and Zr are preferable, and among them, an organic metal compound containing Al is preferable.

  Examples of the aluminum compound applicable to the present invention include aluminum isopolopoxide, aluminum-sec-butylate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, and aluminum tri-n-. Butyrate, aluminum trisec-butyrate, aluminum ethyl acetoacetate diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer and the like. be able to.

  Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butylate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum trisethylacetate) Acetate), aluminum chelate M (aluminum alkyl acetoacetate diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) Ken Fine Chemicals Co., Ltd.), Prenact (registered trademark) AL-M (acetoalkoxy aluminum diisopropylate, manufactured by Ajinomoto Fine Chemicals Co., Ltd.) and the like. It is possible.

  When these compounds are used, they are preferably mixed with a coating solution containing polysilazane under an inert gas atmosphere. This is because these compounds react with moisture and oxygen in the air and suppress the oxidization from proceeding violently. When mixing these compounds with polysilazane, it is preferable to raise the temperature to 30 to 100 ° C. and hold the mixture for 1 minute to 24 hours while stirring.

  The content of the additional metal element in the polysilazane-containing layer constituting the gas barrier film according to the present invention is preferably 0.05 to 10 mol%, more preferably 100 mol%, of silicon (Si). Is 0.5 to 5 mol%.

  In forming the B region using polysilazane, it is preferable to perform a modification treatment after forming the polysilazane-containing layer. The reforming treatment is a treatment for imparting energy to polysilazane to convert a part or all of the polysilazane to silicon oxide or silicon oxynitride.

  For the modification treatment in the present invention, a known method based on a polysilazane conversion reaction can be selected, and examples thereof include a known plasma treatment, a plasma ion implantation treatment, an ultraviolet irradiation treatment, and a vacuum ultraviolet irradiation treatment. In the present invention, a conversion reaction using plasma, ozone, or ultraviolet light capable of performing a conversion reaction at a low temperature is preferable. For plasma and ozone, a conventionally known method can be used. In the present invention, a coating film of a polysilazane-containing coating liquid of a coating method is provided on a base material, and a vacuum ultraviolet irradiation treatment for irradiating a vacuum ultraviolet light (VUV) having a wavelength of 200 nm or less to modify the gas barrier layer is applied. The forming method is preferred.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used, and for example, an excimer lamp (single wavelength of 172 nm, 222 nm, 308 nm, for example, manufactured by Ushio Inc., M.D. Can be mentioned.

  The treatment by irradiation with vacuum ultraviolet rays uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in polysilazane, and preferably uses light energy of a wavelength of 100 to 180 nm. In this method, a silicon oxide film or a silicon oxynitride film is formed at a relatively low temperature (approximately 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.

For details of these reforming treatments, see, for example, paragraphs (0055) to (0091) of JP-A-2012-086394, paragraphs (0049) to (0085) of JP-A-2012-006154, and JP-A-2012-006154. Reference can be made to the contents described in paragraphs (0046) to (0074) of JP-A-2011-251460. The thickness of the B region is not particularly limited, but is preferably in the range of 1 to 500 nm, and more preferably in the range of 10 to 300 nm.
(Formation of mixed area)
As described above, the method of forming the mixed region between the A region and the B region by appropriately adjusting each forming condition when forming the A region and the B region is preferable as the method of forming the mixed region. .

  When the B region is formed by the above-described vapor phase film forming method, for example, a ratio of the non-transition metal (M1) to oxygen in a film forming material, a ratio of an inert gas to a reactive gas during film formation, Mixing by adjusting one or more conditions selected from the group consisting of gas supply amount during film formation, degree of vacuum during film formation, magnetic force during film formation, and power during film formation Regions can be formed.

  When the region B is formed by the above-mentioned coating film forming method, for example, a film forming raw material (such as polysilazane) containing the non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, and a drying temperature A mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method, and reforming conditions.

  When the region A is formed by the above-described vapor deposition method, for example, the ratio of the transition metal (M2) to oxygen in the deposition material, the ratio of the inert gas to the reactive gas during the deposition, By adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation, the mixed region is adjusted. Can be formed.

Note that the thickness of the mixed region can be controlled by the above-described method by appropriately adjusting the formation conditions of the method for forming the A region and the B region. For example, when the region A is formed by a vapor deposition method, a desired thickness can be obtained by controlling the deposition time.
In addition to this, a method of forming a mixed region of the transition metal and the non-transition metals directly is preferable.

As a method for directly forming the mixed region, a known co-evaporation method is preferably used. As such a co-evaporation method, preferably, a co-sputtering method is used. Cosputtered method employed in the present invention include, for example, the composite or a target made of an alloy including both non-transition metal (M1) and the transition metal (M2), the non-transition metal (M1) and the transition metal ( It may be one-source sputtering using a composite target composed of the composite oxide of M2) as a sputtering target.

Moreover, the co-sputtering method of the present invention, alone or its oxide, alone or multi simultaneous sputtering using a plurality of sputtering target containing an oxide thereof of the transition metal (M2) of the non-transition metal (M1) It may be. For a method for producing these sputtering targets and a method for producing a thin film composed of a composite oxide using these sputtering targets, for example, JP-A-2000-160331, JP-A-2004-068109, The description in JP-A-2013-047361 and the like can be appropriately referred to.

  The film forming conditions for performing the co-evaporation method include a ratio of the transition metal (M2) and oxygen in the film forming material, a ratio of an inert gas to a reactive gas during film formation, One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum at the time of film formation, and the electric power at the time of film formation are exemplified. By adjusting the pressure, a thin film made of a composite oxide having an oxygen deficiency composition can be formed. That is, by forming the gas barrier layer using the above-described co-evaporation method, most of the region in the thickness direction of the formed gas barrier layer can be a mixed region. For this reason, according to such a technique, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixing region. In addition, in order to control the thickness of the mixed region, for example, the film formation time when performing the co-evaporation method may be adjusted.

(Adhesive layer)
The thickness of the pressure-sensitive adhesive layer can be appropriately selected in consideration of the intended use of the gas-barrier pressure-sensitive adhesive sheet and the like. Its thickness is usually 0.1 to 1000 μm, preferably 0.5 to 500 μm, more preferably 1 to 100 μm, and still more preferably 1 to 10 μm.

  When it is 0.1 μm or more, a gas-barrier pressure-sensitive adhesive sheet having a sufficient pressure-sensitive adhesive strength can be obtained. When the thickness is 1,000 μm or less, the bending property of the gas barrier pressure-sensitive adhesive sheet is good, and it is advantageous in terms of productivity and handleability.

  The glass transition temperature (Tg) of the polymer component contained in the pressure-sensitive adhesive is preferably in the range of −50 to + 10 ° C., more preferably in the range of −40 to + 10 ° C., and still more preferably in the range of −10 to 0 ° C.

  When the glass transition temperature of the polymer component is within the above range, a tacky adhesive layer having a tack at room temperature is easily obtained, so that the gas barrier pressure-sensitive adhesive sheet is easily attached to an adherend at a temperature near room temperature. can do. For this reason, it is not necessary to heat when sticking the gas barrier pressure-sensitive adhesive sheet, and the problem that the heating lowers the transparency of the electronic member or the optical member or causes the warpage of the adherend is solved. You.

  The mass average molecular weight (Mw) of the polymer component contained in the adhesive is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, and more preferably 500,000 to 2,000. In the range of 1,000,000.

  When the weight average molecular weight (Mw) is within this range, a pressure-sensitive adhesive layer having an excellent balance between adhesive force and cohesive force and having a sufficient anchor effect on an adherend while maintaining flexibility is easily obtained. . For this reason, a gas barrier pressure-sensitive adhesive sheet having excellent durability (bending resistance, heat resistance, and moisture resistance) and excellent adhesion to an adherend can be obtained.

  The molecular weight distribution (Mw / Mn) of the polymer component contained in the pressure-sensitive adhesive is preferably in the range of 1.0 to 5.0, more preferably in the range of 2.0 to 4.5.

  When the molecular weight distribution is equal to or less than the upper limit of the above range, a low molecular weight component is reduced, and a gas barrier pressure-sensitive adhesive sheet having more excellent bending resistance and high-temperature wet heat resistance can be obtained.

  The mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are values in terms of polystyrene measured by gel permeation chromatography (GPC).

  The polymer component contained in the pressure-sensitive adhesive is not particularly limited as long as a desired pressure-sensitive adhesive layer can be formed. Examples of the adhesive containing such a polymer component include known adhesives such as an acrylic adhesive, a rubber adhesive, a polyurethane adhesive, and a silicone adhesive. Among them, acrylic pressure-sensitive adhesives are preferred from the viewpoint of adhesive strength and handleability.

  Examples of the acrylic pressure-sensitive adhesive include those mainly containing a (meth) acrylate-based (co) polymer.

  Examples of the (meth) acrylate-based (co) polymer include a (meth) acrylate homopolymer, a copolymer containing two or more (meth) acrylate units, and a (meth) acrylate. Copolymers with other monomers may be mentioned.

  The copolymer form of the (meth) acrylate copolymer is not particularly limited, and may be any of random, block, and graft copolymers.

  These (meth) acrylate-based (co) polymers may be used alone or in combination of two or more.

  In addition, "(meth) acrylic acid" represents acrylic acid or methacrylic acid, and "(co) polymer" represents a homopolymer or a copolymer.

  Examples of the (meth) acrylate monomer used when synthesizing the (meth) acrylate ester (co) polymer include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group. Can be

  Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate , Pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate , Palmityl (meth) acrylate, stearyl (meth) acrylate and the like.

  Other monomers used when synthesizing a copolymer of (meth) acrylic acid ester and another monomer include monomers having a crosslinkable functional group such as a hydroxyl group, a carboxyl group, and an amino group; Vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; dienes such as butadiene, isoprene and chloroprene; acrylonitrile and methacrylonitrile And acrylamides such as acrylamide, N-methylacrylamide, and N, N-dimethylacrylamide.

Examples of the monomer having a crosslinkable functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate , Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) Monoalkylaminoalkyl (meth) acrylates such as acrylate and monoethylaminopropyl (meth) acrylate; ethylenic amino acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid And the like; sum carboxylic acid.
These may be used alone or in combination of two or more.

  The content of the repeating unit derived from another monomer in the (meth) acrylate-based (co) polymer is preferably 0.01 to 10% by mass, more preferably 0 to 10% by mass, based on all repeating units. 0.05 to 7.0% by mass.

  When the content of the monomer unit is 0.01% by mass or more, a sufficient cross-linking can be performed by a reaction with a cross-linking agent described later, and a pressure-sensitive adhesive layer having more excellent durability can be obtained. On the other hand, when the content is 10% by mass or less, the degree of crosslinking does not become too high, so that a pressure-sensitive adhesive layer having sufficient adhesiveness to an adherend can be obtained.

  The (meth) acrylate-based (co) polymer can be obtained by a known polymerization method such as a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.

  When a (meth) acrylate-based (co) polymer having a crosslinkable functional group is used as the pressure-sensitive adhesive component, a crosslinker may be used in combination.

  Examples of the crosslinking agent include isocyanate-based crosslinking agents such as tolylene diisocyanate, hexamethylene diisocyanate, and their adducts such as trimethylolpropane tolylene diisocyanate; epoxy-based crosslinking agents such as ethylene glycol glycidyl ether; hexa [1- (2-methyl) -aziridinyl] aziridine-based cross-linking agents such as trifosphatriazine; chelate-based cross-linking agents such as aluminum chelates; and the like.

  These may be used alone or in combination of two or more.

  The amount of the crosslinking agent to be used is generally 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the (meth) acrylate-based (co) polymer.

  As the rubber-based pressure-sensitive adhesive, a modified natural rubber-based pressure-sensitive adhesive obtained by graft-polymerizing one or more monomers selected from natural rubber, alkyl (meth) acrylate, styrene, and (meth) acrylonitrile on natural rubber. Rubber-based pressure-sensitive adhesives composed of isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, urethane rubber, polyisobutylene-based resin, polybutene resin, and the like. Among them, polyisobutylene-based resins are preferred.

  Examples of the silicone-based pressure-sensitive adhesive include those containing dimethylsiloxane as a main component.

  The pressure-sensitive adhesive used in the present invention may contain an active energy ray-curable compound. By containing the active energy ray-curable compound, the storage elastic modulus of the pressure-sensitive adhesive layer at a high temperature (80 ° C.) is hardly reduced, and the gas-barrier pressure-sensitive adhesive sheet and an electronic member or an optical member provided with the same are subjected to high-temperature or high-humidity conditions. When placed below, the interface of the pressure-sensitive adhesive layer can be more effectively prevented from peeling off.

  Examples of the active energy ray-curable compound include a polyfunctional (meth) acrylate-based monomer, an active energy ray-curable acrylate-based oligomer, and an adduct acrylate-based polymer having a group having a (meth) acryloyl group introduced into a side chain. No.

  These may be used alone or in combination of two or more.

  Examples of the polyfunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol di ( (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphorus Bifunctional types such as acid di (meth) acrylate, di (acryloyloxyethyl) isocyanurate, allylated cyclohexyldi (meth) acrylate; trimethylolpropane tri (meth) acrylate Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate Trifunctional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; pentafunctional types such as propionic acid-modified dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meta) And 6) functional groups such as acrylates and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  These may be used alone or in combination of two or more.

  Among these, those having a cyclic structure in the molecule are preferable. The cyclic structure may be a carbocyclic structure or a heterocyclic structure, and may be a monocyclic structure or a polycyclic structure.

  Examples of polyfunctional (meth) acrylate monomers having a cyclic structure in the molecule include those having an isocyanurate structure such as di (acryloyloxyethyl) isocyanurate and tris (acryloyloxyethyl) isocyanurate; dimethylol dicyclo Pentane diacrylate; ethylene oxide-modified hexahydrophthalic acid diacrylate; tricyclodecane dimethanol acrylate; neopentyl glycol-modified trimethylolpropane diacrylate; adamantane diacrylate;

  The molecular weight of the polyfunctional (meth) acrylate monomer is preferably less than 1,000.

  Examples of the active energy ray-curable acrylate oligomer include a polyester acrylate oligomer, an epoxy acrylate oligomer, a urethane acrylate oligomer, a polyol acrylate oligomer, a polybutadiene acrylate oligomer, and a silicone acrylate oligomer.

  As the polyester acrylate oligomer, the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol is esterified with (meth) acrylic acid, or Compounds obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid are exemplified.

  Examples of the epoxy acrylate oligomer include compounds obtained by reacting (meth) acrylic acid with an oxirane ring of a relatively low-molecular-weight bisphenol-type epoxy resin or a novolak-type epoxy resin to cause esterification.

  A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic anhydride can also be used.

  Examples of the urethane acrylate oligomer include a compound obtained by esterifying a polyurethane oligomer obtained by a reaction between a polyether polyol or a polyester polyol and a polyisocyanate with (meth) acrylic acid.

  Examples of the polyol acrylate-based oligomer include a compound obtained by esterifying a hydroxyl group of a polyether polyol with (meth) acrylic acid.

  Examples of the polybutadiene acrylate oligomer include acrylate oligomers having an acrylate group at a terminal or a side chain of the polybutadiene oligomer.

  Examples of the silicone acrylate oligomer include an acrylate oligomer having a polysiloxane bond in the main chain.

  These acrylate oligomers may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the acrylate oligomer is preferably 50,000 or less, more preferably 500 to 50,000, and still more preferably 3,000 to 40,000. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  As the adduct acrylate-based polymer having a group having a (meth) acryloyl group introduced into a side chain, the (meth) acrylate described in the above (meth) acrylate-based (co) polymer and the (meth) acrylate in the molecule Using a copolymer with a monomer having a crosslinkable functional group, a compound having a (meth) acryloyl group and a group reactive with the crosslinkable functional group in a part of the crosslinkable functional group of the copolymer is reacted. Can be obtained.

  The weight average molecular weight (Mw) of such an adduct acrylate-based polymer is preferably in the range of 100,000 to 2,000,000. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  The content ratio of the resin component to the active energy ray-curable compound is preferably 100: 1 to 100: 100, more preferably 100: 5 to 100: 50, by mass ratio (resin component: active energy ray-curable compound). And more preferably in the range of 100: 10 to 100: 20.

  Further, in the pressure-sensitive adhesive containing the active energy ray-curable compound, a photopolymerization initiator can be contained as required.

  Examples of the photopolymerization initiator include, for example, bensoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylamido Benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-Diethylthioxanthone, benzyldimethylketal, acetophenonedimethylketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl] propanone], 2,4 , 6-trimethylbenzoyl-diphenylphosphine oxide.

  These may be used alone or in combination of two or more.

  The compounding amount of the photopolymerization initiator is usually in the range of 0.2 to 20 parts by mass based on 100 parts by mass of the active energy ray-curable compound.

  Examples of the active energy rays to be irradiated include ultraviolet rays and electron beams, and ultraviolet rays are preferred.

When irradiating ultraviolet rays, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like can be used. The irradiation amount is usually in the range of illuminance 50 to 1000 mW / cm ² and light amount 50 to 3000 mJ / cm ² .

  The irradiation time is usually from 0.1 to 1000 seconds, preferably from 1 to 500 seconds, more preferably from 10 to 100 seconds. Irradiation may be performed a plurality of times in order to satisfy the above-mentioned light amount in consideration of the heat load in the ultraviolet irradiation step.

  When irradiating an electron beam, an electron beam accelerator or the like can be used. The irradiation dose is usually in the range of 10 to 1000 krad.

  The irradiation time is usually from 0.1 to 1000 seconds, preferably from 1 to 500 seconds, more preferably from 10 to 100 seconds.

  When an electron beam is used, the pressure-sensitive adhesive layer can be formed without adding a photopolymerization initiator.

  The pressure-sensitive adhesive used in the present invention may contain a silane coupling agent, an alkoxy metal compound, or the like.

  By containing a silane coupling agent or an alkoxy metal compound, particularly when a silicon-containing compound is used as the material of the gas barrier layer, or when the adherend is a glass surface, the pressure-sensitive adhesive layer and the gas barrier layer During this time, the adhesion between the pressure-sensitive adhesive layer and the adherend becomes better.

  Examples of the silane coupling agent include silicon compounds having a polymerizable unsaturated group such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- (3,4 Silicon compounds having an epoxy structure such as -epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Amino-containing silicon compounds such as -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; and the like.

  Examples of the alkoxy metal compound include titanate-based coupling agents, aluminate-based coupling agents, and zirconium-based coupling agents.

  These may be used alone or in combination of two or more.

  The addition amount of the silane coupling agent or the alkoxy metal compound is preferably in the range of 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, based on 100 parts by mass of the solid content of the pressure-sensitive adhesive.

  The pressure-sensitive adhesive used in the present invention may further contain various additives. Examples of the additive include a light stabilizer, an antioxidant, a tackifier, a plasticizer, an ultraviolet absorber, a colorant, a resin stabilizer, a filler, a pigment, a bulking agent, and an antistatic agent.

  In addition, the storage elastic modulus at 23 ° C. of the pressure-sensitive adhesive layer in the gas-barrier pressure-sensitive adhesive sheet of the present invention is 1.5 × 104 to 1.0 × from the viewpoint of adhesive strength, bending resistance, heat resistance, moisture resistance and the like. It is preferably in the range of 107 Pa, and more preferably in the range of 6.0 × 104 to 1.0 × 106 Pa.

  The storage elastic modulus at 80 ° C. of the pressure-sensitive adhesive layer is determined from the viewpoint of preventing the interface of the pressure-sensitive adhesive layer from peeling off when the electronic member or the optical member is subjected to high temperature or high humidity conditions. 0 × 103 to 1.0 × 106 Pa is preferable, 1.0 × 104 to 8.0 × 105 Pa is more preferable, and the range of 2.0 × 104 to 5.0 × 105 Pa is further preferable.

  The storage elastic modulus of the pressure-sensitive adhesive layer is a value measured at a frequency of 1 Hz by a torsional shear method using a dynamic viscoelasticity measuring device in accordance with JIS K7244.

  The method for forming the pressure-sensitive adhesive layer is not particularly limited, and a known method can be used.

  For example, a pressure-sensitive adhesive, and, if desired, a pressure-sensitive adhesive layer-forming solution containing a solvent or the like is applied by a known coating method, and the obtained coating film is dried, and if necessary, heated or irradiated with active energy rays. And the formation method.

  As the application and drying methods, the methods described in the method for forming a gas barrier layer can be used.

(Protective layer)
The gas barrier pressure-sensitive adhesive sheet of the present invention may have a protective layer. The protective layer is a layer having a role of protecting the gas barrier layer when an external impact is applied.

  The position where the protective layer is laminated is not particularly limited, but is preferably laminated adjacent to the gas barrier layer.

  As the protective layer, those having good transparency and good scratch resistance are preferable. In addition, when the protective layer is disposed on the outermost surface when incorporated into an electronic device or an optical device, the protective layer has functions such as antifouling property, antifingerprint resistance, antistatic property, water repellency, and hydrophilicity. Is preferred.

  The thickness of the protective layer can be appropriately selected in consideration of the purpose of use of the gas barrier pressure-sensitive adhesive sheet and the like. The thickness is usually 0.05 to 20 μm, preferably 0.1 to 10 μm, more preferably 0.2 to 8.0 μm, and still more preferably 0.2 to 6.0 μm.

  If it is 0.05 μm or more, the scratch resistance becomes sufficient. When the thickness is 10 μm or less, curling due to distortion during curing hardly occurs.

  The surface roughness Ra (arithmetic mean roughness) of the protective layer is preferably 5.0 nm or less, more preferably 3.0 nm or less, and even more preferably 2.0 nm or less. Further, the surface roughness Rt (maximum sectional height) is preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less.

  When the surface roughnesses Ra and Rt exceed 10.0 nm and 100 nm, respectively, the surface roughness of the gas barrier layer and the pressure-sensitive adhesive layer increases, and the gas barrier properties of the gas-barrier pressure-sensitive adhesive sheet may be reduced.

  The surface roughnesses Ra and Rt are values obtained by measuring a range of 10 μm square using AFM.

  The material of the protective layer is not particularly limited, and known materials can be used. For example, a silicon-containing compound; a photopolymerizable compound comprising a photopolymerizable monomer and / or a photopolymerizable prepolymer; and a polymerizable composition containing a polymerization initiator that generates a radical by at least light in a visible light region; , Polyurethane resins (especially two-component curing resins of isocyanate compounds with polyacryl polyols, polyester polyols, polyether polyols, etc.), acrylic resins, polycarbonate resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral resins And nitrocellulose-based resins; alkyl titanates; ethylene imines;

  These may be used alone or in combination of two or more.

  Above all, as a material of the protective layer, a photopolymerizable compound composed of a photopolymerizable monomer and / or a photopolymerizable prepolymer, and a radical at least in the visible light region, because of its excellent transparency and scratch resistance. A polymerizable composition containing a polymerization initiator that generates the following is preferred.

  As the photopolymerizable compound and the polymerization initiator, the active energy ray-curable compounds and the photopolymerization initiator exemplified in the section of the pressure-sensitive adhesive can be used.

  The protective layer is formed by applying a solution for forming a protective layer obtained by dissolving or dispersing the above-described material in an appropriate solvent by a known method, drying the obtained coating film, and, if desired, heating or irradiating light. Can be formed.

  As the application and drying methods, the methods described in the method for forming a gas barrier layer can be used.

(Conductor layer)
The gas barrier pressure-sensitive adhesive sheet of the present invention may have a conductor layer. The conductor layer is a layer having conductivity, and is a layer provided in an electronic member or the like for use as an electrode or for improving antistatic properties and heat dissipation.

  The position where the conductor layer is laminated can be selected according to the purpose of using the gas barrier pressure-sensitive adhesive sheet of the present invention, and is not particularly limited.

  The surface resistivity of the conductor layer is preferably 1,000 Ω / □ or less, more preferably 200 Ω / □ or less.

  The thickness of the conductor layer can be appropriately selected in consideration of the intended use of the gas barrier pressure-sensitive adhesive sheet and the like. Its thickness is usually from 10 nm to 9 μm, preferably from 20 nm to 1.0 μm.

  Examples of the material of the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, tin oxide (ATO) doped with antimony; tin oxide (FTO) doped with fluorine; metals such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide (IZO) Oxides; metals such as gold, silver, chromium and nickel; mixtures of these metals with metal oxides; inorganic conductive substances such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene and polypyrrole; Is mentioned.

  Among these, metal oxides are preferable from the viewpoint of transparency, and indium oxide-based and zinc oxide-based metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and zinc indium oxide (IZO) are particularly preferable. preferable.

  Examples of the method for forming the conductor layer include an evaporation method, a sputtering method, an ion plating method, a thermal CVD method, and a plasma CVD method. Among these, a sputtering method is preferable because a conductor layer can be easily formed.

  The formed conductor layer may be patterned as needed. Examples of the patterning method include chemical etching by photolithography and the like, physical etching using a laser and the like, vacuum evaporation using a mask, sputtering, lift-off, printing, and the like.

(Release sheet)
The gas barrier pressure-sensitive adhesive sheet of the present invention may have a release sheet. The release sheet is laminated on the outermost layer of the gas barrier pressure-sensitive adhesive sheet, and when storing and transporting the gas barrier pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer, the gas barrier layer, and the role of protecting the other layers described above and Immediately before the use of the gas-barrier pressure-sensitive adhesive sheet, it has a role of imparting supportability and is peeled off before sticking.

  The gas barrier pressure-sensitive adhesive sheet of the present invention may have a release sheet on one side, or may have two types of release sheets, a first release sheet and a second release sheet, on both sides. Good. In the latter case, it is preferable to use two types of release sheets so that the release sheet to be released first can be released more easily.

  Further, as described later, in the method for producing a gas-barrier pressure-sensitive adhesive sheet of the present invention, the gas-barrier pressure-sensitive adhesive sheet is used for forming a gas barrier layer and a pressure-sensitive adhesive layer.

  The release sheet is obtained by applying a release agent to a release substrate such as paper or a plastic film and providing a release agent layer.

  Examples of the release substrate include paper substrates such as glassine paper, coated paper and woodfree paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene on these paper substrates; cellulose, starch, polyvinyl Paper substrates treated with fillers such as alcohols and acrylic-styrene resins; plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; and polyolefin films such as polyethylene and polypropylene.

  Examples of the release agent include olefin resins such as polyethylene and polypropylene; rubber elastomers such as isoprene resin and butadiene resin; long-chain alkyl resins; alkyd resins; fluororesins; silicone resins; No.

  The thickness of the release agent layer is not particularly limited, but is preferably 0.02 to 2.0 μm, more preferably 0.05 to 1.5 μm when the release agent is applied in a solution state.

  The surface roughness Ra of the release sheet is preferably 10.0 nm or less, more preferably 8.0 nm or less. The surface roughness Rt is preferably 100 nm or less, more preferably 50 nm or less.

  When the surface roughnesses Ra and Rt exceed 10.0 nm and 100 nm, respectively, the surface roughness of the laminated gas barrier layer or pressure-sensitive adhesive layer increases, and the gas barrier properties of the gas-barrier pressure-sensitive adhesive sheet may be reduced. There is.

  In particular, in the method for producing a gas-barrier pressure-sensitive adhesive sheet described below, in the step of forming a gas barrier layer or a pressure-sensitive adhesive layer on a release sheet, the surface roughness of the release agent layer is transferred to the gas barrier layer or the pressure-sensitive adhesive layer. It is preferable that the surface roughnesses Ra and Rt of the release sheet be within the above-mentioned ranges.

  The conditions for measuring the surface roughness are the same as those described above for the surface roughness of the protective layer.

  The method for producing the gas barrier pressure-sensitive adhesive sheet of the present invention is not particularly limited, and a conventionally known method can be employed. Among them, a method using a release sheet is preferable because a gas-barrier pressure-sensitive adhesive sheet can be efficiently and easily manufactured.

  The method for producing a gas-barrier pressure-sensitive adhesive sheet of the present invention is characterized by including a step of forming a pressure-sensitive adhesive layer or a gas barrier layer on a surface of a release sheet having releasability.

The method for producing a gas barrier pressure-sensitive adhesive sheet of the present invention preferably includes the following steps 1 to 3. The details of the method for forming the gas barrier layer are as described above.
Step 1: Forming a gas barrier layer on a release substrate of the first release sheet to obtain a release sheet with a gas barrier layer Step 2: Substrate having release characteristics of the second release sheet Step 3: forming a pressure-sensitive adhesive layer thereon to obtain a release sheet with a pressure-sensitive adhesive layer Step 3: the release sheet with a gas-barrier layer and the release sheet with a pressure-sensitive adhesive layer, the gas-barrier layer and the pressure-sensitive adhesive layer For example, the gas barrier pressure-sensitive adhesive sheet S1 shown in FIG. 1A can be obtained by the following steps A1 to A3.
Step A1: Step of forming a gas barrier layer on the release layer surface of the first release sheet to obtain a release sheet with a gas barrier layer (Step 1)
Step A2: Step of forming an adhesive layer on the release layer surface of the second release sheet to obtain a release sheet with an adhesive layer (Step 2)
Step A3: A step of bonding the pressure-sensitive adhesive layer of the release sheet with the pressure-sensitive adhesive layer to the gas barrier layer of the release sheet with the gas barrier layer (step 3).
The gas barrier pressure-sensitive adhesive sheet 5B shown in FIG. 1B can be obtained by the following steps B1 and B2.
Step B1: A step of forming an adhesive layer on the release layer surface of the release sheet to obtain a release sheet with an adhesive layer (Step 2)
Step B2: Peeling off the release sheet on the gas barrier layer side of the gas barrier pressure-sensitive adhesive sheet obtained in Steps A1 to A3, and adhesion between the exposed gas barrier layer and the release sheet with the pressure-sensitive adhesive layer obtained in Step B1 Step of bonding with agent layer (Step 1, Step 3)
The gas barrier pressure-sensitive adhesive sheet 5C shown in FIG. 1C can be obtained by the following steps C1 to C4.
Step C1: A protective layer is formed on the release layer surface of the first release sheet to obtain a release sheet with a protective layer. Step C2: A gas barrier layer is formed on the protective layer of the release sheet with a protective layer obtained in Step C1. Step of Forming (Step 1)
Step C3: a step of forming an adhesive layer 2a on the release layer surface of the second release sheet to obtain a release sheet with an adhesive layer (Step 2)
Step C4: a step of bonding the gas barrier layer formed in step C2 and the pressure-sensitive adhesive layer formed in step C3 (step 3)
The gas barrier pressure-sensitive adhesive sheet 5D shown in FIG. 1D can be obtained by the following steps D1 to D3.
Step D1: a step of forming an adhesive layer on the release layer surface of the first release sheet to obtain a release sheet with an adhesive layer (step 2)
Step D2: Two gas-barrier pressure-sensitive adhesive sheets are produced by the steps C1 to C4, and a release sheet on the pressure-sensitive adhesive layer side of the first gas-barrier pressure-sensitive adhesive sheet and a protective layer side of the second gas-barrier pressure-sensitive adhesive sheet. Of the first gas-barrier pressure-sensitive adhesive sheet and the protective layer of the second gas-barrier pressure-sensitive adhesive sheet, and then (peeling sheet / protective layer / gas barrier layer / adhesive). (Layer / Protective Layer / Gas Barrier Layer / Adhesive Layer / Release Sheet) (Steps 1 and 3)
Step D3: a step of peeling off the release sheet on the protective layer side of the laminate obtained in step D2 and bonding the exposed protective layer to the pressure-sensitive adhesive layer of the release sheet with a pressure-sensitive adhesive layer obtained in step D1. By using the method for producing a gas-barrier pressure-sensitive adhesive sheet of the present invention, the gas-barrier pressure-sensitive adhesive sheet of the present invention can be efficiently produced.

《Electronic device》
The gas-barrier pressure-sensitive adhesive sheet of the present invention can be preferably applied to devices whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.) in the air. That is, the gas barrier film of the present invention can be applied to an electronic device including an electronic device body.

  Examples of the electronic device main body used in the electronic device provided with the gas barrier pressure-sensitive adhesive sheet of the present invention include, for example, a QD film having a quantum dot (QD) -containing resin layer, an organic electroluminescent element (organic EL element), and a liquid crystal. Examples include a display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

[Quantum dot (QD) -containing resin layer]
The gas barrier pressure-sensitive adhesive sheet of the present invention can be applied to a QD film having a quantum dot (QD) -containing resin layer.

  Hereinafter, a quantum dot (QD), a resin, and the like, which are main components of the QD-containing resin layer, will be described.

<Quantum dots>
In general, a semiconductor nanoparticle having a quantum confinement effect in a nanometer-sized semiconductor material is also referred to as a “quantum dot”. Such a quantum dot is a small lump of about several tens of nanometers in which hundreds to thousands of semiconductor atoms are gathered. When the quantum dot reaches an energy excited state by absorbing light from an excitation source, the energy of the quantum dot becomes large. Emit energy corresponding to the band gap.

  Therefore, it is known that quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) various wavelengths and colors can be emitted by controlling the size of the particles, and (2) fine particles of various sizes with a broad absorption band and a single wavelength of excitation light. It can emit light, (3) it has a good symmetric fluorescence spectrum, and (4) it has excellent durability and fading resistance as compared with organic dyes.

  The quantum dots contained in the QD-containing resin layer may be known, and can be generated using any method known to those skilled in the art. For example, suitable QDs and methods for forming suitable QDs include U.S. Patent No. 6,225,198, U.S. Patent Application Publication No. 2002/0066401, U.S. Patent Nos. 6,207,229, and 6,322,901. No. 6,949,206, No. 7,572,393, No. 7,267,865, No. 7,374,807, U.S. Patent Application No. 11 / 299,299, and U.S. Patent No. 6,861,155. One.

  The QD is made from any suitable material, preferably an inorganic material, and more preferably an inorganic conductor or semiconductor material. Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.

Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeSe , BeTe, MgS, MgSe, GeS , GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4, Ge 3 N 4, Al 2 O 3, _{(Al, Ga, In) 2} (S, Se, Te) 3, Al 2 O, and include but are more than one suitable combination of such semiconductor, and the like.

  In the present invention, the following core / shell type quantum dots, for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS and the like can also be preferably used.

<resin>
In the QD-containing resin layer, a resin can be used as a binder for holding the quantum dots. For example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate pro Cellulose esters such as pionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyetherketone, polyetherketoneimide And acrylic resins such as polyamide resins, fluororesins, nylons, and polymethyl methacrylate.

  The QD-containing resin layer preferably has a thickness in the range of 50 to 200 μm.

  The content of the quantum dots in the QD-containing resin layer varies depending on the compound to be used, but is generally preferably in the range of 15 to 60% by volume.

[Organic EL device]
The gas-barrier pressure-sensitive adhesive sheet of the present invention can be applied to an organic EL device, and for the outline of the organic EL device applicable to the present invention, for example, JP-A-2013-157634, JP-A-2013-168552 JP, 2013-177361, JP, 2013-187221, JP, 2013-191644, JP, 2013-191804, JP, 2013-225678, JP, 2013-235994, JP 2013-243234 A, JP 2013-243236 A, JP 2013-242366 A, JP 2013-243371 A, JP 2013-245179 A, JP 2014-003249 A, JP JP 2014-003299 A, JP 2014-0113910 A , It may be mentioned JP 2014-017493 discloses a configuration described in JP-2014-017494 Patent Publication.

  FIG. 3 is an example of a cross-sectional view showing a configuration of an organic EL element which is an embodiment of the electronic device of the present invention. On the base 31, a gas barrier layer 32, a first electrode 33, an organic EL layer 34, a second electrode 35, an inorganic sealing layer 36, an adhesive layer 37, a gas barrier layer 38, and a protective layer 39 are shown in FIG. It is configured to be.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, “parts” or “%” is used, but “parts by mass” or “% by mass” is used unless otherwise specified.

<Release film>
As a release film, a release film (non-silicone type, a film having a release layer on one side of a polyethylene terephthalate film having a thickness of 50 μm) manufactured by Fujimori Kogyo KK was used.

<Coating solution for adhesive layer>
Ethyl acetate of an acrylate-based copolymer (mass average molecular weight of about 1.2 million) obtained by polymerizing n-butyl acrylate and acrylic acid with n-butyl acrylate: acrylic acid (mass ratio) = 95: 5 15 parts by mass of EO-modified diisocyanuric acid and triacrylate, 100 parts by mass of a solution (solid concentration: 18%), 0.3 parts by mass of a photopolymerization initiator (IRGACURE500, manufactured by Ciba Japan), and trimethylolpropane tolylenediene One part by mass of isocyanate (trade name “Coronate L”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added and mixed in terms of solid content. Next, 0.1 part by mass of 3-glycidoxypropyltrimethoxysilane was added and mixed to obtain an adhesive layer coating solution.

<Release film for forming hard coat layer>
On the release layer of the release film, a hard coat layer was formed as described below.

UV curing resin Opstar (registered trademark) Z7527 manufactured by JSR Co., Ltd. is applied to a dry film thickness of 5 μm, dried at 80 ° C., and then irradiated with air using a high-pressure mercury lamp under air. Curing was performed under the condition of 0.8 J / cm ² . Thus, a hard coat layer-forming release film was obtained.

<Adhesive layer forming release film>
On the release layer of the release film, a pressure-sensitive adhesive layer coating solution was applied to a dry film thickness of 20 μm, and dried at 80 ° C. for 5 minutes. Next, curing was performed using a high-pressure mercury lamp under the conditions of an irradiation energy amount of 0.3 J / cm ² . Thus, a pressure-sensitive adhesive layer-forming release film was obtained.

<Preparation of gas barrier pressure-sensitive adhesive sheet 1>
A gas barrier layer was formed on the hard coat layer of the release film on which the hard coat layer was formed as follows.

A silicon oxide layer having a thickness of 100 nm was formed using a magnetron sputtering device. A commercially available polycrystalline Si target was used as a target, and a film was formed by an RF method with a film formation time set to a thickness of 100 nm. Argon and oxygen were used as process gases, and the oxygen partial pressure was adjusted so that the composition of silicon oxide was SiO ₂ .

  The composition profile of this gas barrier layer in the thickness direction was determined by XPS analysis. Table 1 shows the presence / absence of the mixed region according to the present invention, the thickness of the mixed region, and the minimum value of the calculation result relating to the relational expression (2) of the present invention in the mixed region (hereinafter similarly shown in Table 1).

  Next, the gas barrier layer surface of the hard coat layer-forming release film on which the gas barrier layer is formed and the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive layer-forming release film are opposed to each other, and are bonded at room temperature (25 ° C.) using a roll laminator. A barrier pressure-sensitive adhesive sheet 1 was obtained.

<Preparation of gas barrier pressure-sensitive adhesive sheet 2>
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20) and an amine catalyst (N, N, N ', N'-tetramethyl-1,6-diaminohexane (TMDAH) )) And 20% by weight of a dibutyl ether solution of perhydropolysilazane (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1 (mass ratio), and further for adjusting the dry film thickness. The mixture was diluted with dibutyl ether to prepare a coating solution having a solid content of 4% by mass.

  On the hard coat layer of the release film formed with the hard coat layer, a coating solution was applied by spin coating so that the thickness after drying became 100 nm, and dried at 80 ° C. for 2 minutes to obtain a polysilazane-containing coating film. .

  A plasma ion implanter (RF power supply: model number “RF” 56000, manufactured by JEOL; high-voltage pulse power supply: “PV-3-HSHV-0835”, manufactured by Kurita Manufacturing Co., Ltd.) is applied to the coating film. Under the conditions of a gas flow rate of 100 sccm, a duty ratio of 0.5%, an applied voltage of −6 kV, a frequency of 13.56 MHz, an applied power of 1000 W, a chamber inner pressure of 0.2 Pa, a pulse width of 5 μsec, and a processing time of 200 seconds, a gas derived from argon gas (Ar) is used. Ions were implanted into the surface of the polysilazane-containing coating to form a gas barrier layer.

  Next, a gas barrier pressure-sensitive adhesive sheet 2 was obtained in the same manner as the gas barrier pressure-sensitive adhesive sheet 1.

<Preparation of gas barrier pressure-sensitive adhesive sheet 3>
In the same manner as in the gas barrier pressure-sensitive adhesive sheet 2, a polysilazane-containing coating film (B region precursor) was obtained.

  A 10 nm-thick niobium oxide layer (region A) was formed on this coating using a magnetron sputtering apparatus. A commercially available oxygen-deficient niobium pentoxide target was used as a target, and a film was formed by a DC method with a film formation time set to a thickness of 10 nm. Argon and oxygen were used as process gases, and the oxygen partial pressure was adjusted to 12%. Thus, a gas barrier layer was formed.

  Next, a gas barrier pressure-sensitive adhesive sheet 3 was obtained in the same manner as the gas barrier pressure-sensitive adhesive sheet 1.

<Preparation of gas barrier adhesive sheet 4>
A gas-barrier pressure-sensitive adhesive sheet 4 was obtained in the same manner as the gas-barrier pressure-sensitive adhesive sheet 3, except that the niobium oxide layer was formed by setting the film-forming time so as to have a thickness of 5 nm.

<Preparation of gas barrier pressure-sensitive adhesive sheet 5>
A gas-barrier pressure-sensitive adhesive sheet 5 was obtained in the same manner as the gas-barrier pressure-sensitive adhesive sheet 3 except that the niobium oxide layer was formed by setting the film-forming time so as to have a thickness of 2 nm.

<Preparation of gas-barrier pressure-sensitive adhesive sheet 6>
A gas-barrier pressure-sensitive adhesive sheet 6 was obtained in the same manner as the gas-barrier pressure-sensitive adhesive sheet 3 except that the niobium oxide layer was formed by setting the film-forming time so as to have a thickness of 0.5 nm.

<Preparation of gas barrier pressure-sensitive adhesive sheet 7>
A gas barrier pressure-sensitive adhesive sheet 7 was obtained in the same manner as the gas barrier pressure-sensitive adhesive sheet 3 except that a 10 nm-thick tantalum oxide layer was formed instead of the niobium oxide layer.

  Specifically, a commercially available metal tantalum target was used as a target, and a film was formed by a DC method with a film formation time set to a thickness of 10 nm. Argon and oxygen were used as the process gas, and the oxygen partial pressure was adjusted to 20%. Thus, a gas barrier layer was formed.

<Preparation of gas barrier pressure-sensitive adhesive sheet 8>
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (AZ120-20, manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst (N, N, N ', N'-tetramethyl-1,6-diaminohexane (TMDAH) )) And 20% by mass of a dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing perhydropolysilazane were mixed at a ratio of 4: 1 (mass ratio), and the solid content concentration was further mixed with dibutyl ether. Was prepared so as to be 4% by mass. Preparation of the coating solution was performed in a glove box. Next, an aluminum compound liquid was prepared by diluting aluminum ethyl acetoacetate diisopropylate with dibutyl ether so as to have a solid concentration of 4% by mass. The liquid A and the aluminum compound liquid are mixed so that the Al / Si atomic ratio becomes 0.01, the temperature is raised to 80 ° C. with stirring, and the temperature is maintained at 80 ° C. for 2 hours, and then to room temperature (25 ° C.). Cooled slowly. Thus, a coating solution having a solid content of 4% by mass was prepared.

  On the hard coat layer of the release film formed with the hard coat layer, a coating solution was applied by spin coating so that the thickness after drying became 100 nm, and dried at 80 ° C. for 2 minutes to obtain a polysilazane-containing coating film. .

The coating film was subjected to vacuum ultraviolet irradiation using a vacuum ultraviolet irradiation device having a Xe excimer lamp with a wavelength of 172 nm and an irradiation energy of 0.5 J / cm ² . At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The temperature of the stage on which the sample was placed was 80 ° C.

  Next, a niobium oxide layer was formed in the same manner as the gas-barrier pressure-sensitive adhesive sheet 3, and further bonded to a pressure-sensitive adhesive layer-forming release film to obtain a gas-barrier pressure-sensitive adhesive sheet 8.

<Preparation of gas barrier pressure-sensitive adhesive sheet 9>
A gas-barrier pressure-sensitive adhesive sheet 9 was obtained in the same manner as the gas-barrier pressure-sensitive adhesive sheet 8, except that the niobium oxide layer was not formed.

<Preparation of gas barrier film>
The following three types were prepared as substrates for gas barrier films. The release film on the pressure-sensitive adhesive layer side of each of the gas-barrier pressure-sensitive adhesive sheets is peeled off, and the pressure-sensitive adhesive layer and the following substrate surface (substrates 2 and 3 on which a concavo-convex layer is formed) are opposed to each other using a roll laminator Lamination was performed at room temperature (25 ° C.). Next, the release film on the hard coat layer side was peeled off to obtain a gas barrier film.

<Substrate 1>
A 100 μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (U403), manufactured by Toray Industries, Inc.), on both surfaces of which an easy adhesion treatment was performed, was used.

<Substrate 2>
One side of the substrate 1 was coated with the following uneven layer coating solution 1 so that the dry coverage was 1.5 g / m ^2, and dried at 80 ° C. for 5 minutes to obtain a substrate 2. This is a substrate for evaluating the presence or absence of deterioration in gas barrier properties when bonded to an uneven surface of an electronic device or the like.
Uneven layer coating solution 1
65 parts by mass of a colloidal silica aqueous dispersion (Snowtex XS, solid content 20% by mass, manufactured by Nissan Chemical Co., Ltd.), 37 parts by mass of acrylic emulsion (AE986B, solid content 35% by mass, manufactured by E-Tech Co., Ltd.), cross-linking with an average particle diameter of 10 μm 3 parts by mass of acrylic particles (MX-1000, manufactured by Soken Chemical Co., Ltd.) were sufficiently mixed and diluted with pure water to obtain a coating solution having a solid content of 5% by mass.

<Substrate 3>
One side of the substrate 1 was coated with the following uneven layer coating solution 2 so that the dry coverage was 2.0 g / m ^2, and dried at 80 ° C. for 5 minutes to obtain a substrate 3. This is a substrate for evaluating the presence / absence of deterioration in gas barrier properties when the substrate is bonded to an uneven surface of an electronic device or the like, similarly to the substrate 2.

<Coating liquid for uneven layer 2>
65 parts by mass of colloidal silica aqueous dispersion (Snowtex XS, solid content: 20% by mass, manufactured by Nissan Chemical Co., Ltd.), 37 parts by mass of acrylic emulsion (AE986B, solid content: 35% by mass, manufactured by E-Tech Co., Ltd.) 3 parts by mass of acrylic particles (MX-1500H, manufactured by Soken Chemical Co., Ltd.) were sufficiently mixed and diluted with pure water to obtain a coating solution having a solid content of 5% by mass.
<Evaluation of water vapor transmission rate>
The water vapor transmission rate of each gas barrier film was measured at 38 ° C. and 100% RH using a water vapor transmission rate measuring apparatus, Aquatran manufactured by Mocon. At this time, the gas barrier film was set so that the detection side of the device was the hard coat layer surface of the gas barrier film. The results are shown in Table X.

  As can be seen from Table 1, the gas-barrier pressure-sensitive adhesive sheet of the present invention has good gas-barrier properties, and deteriorates even when pressure-bonded to a substrate having irregularities. It turns out that there is almost no.

2, 2a, 2b: Gas barrier layer 3, 3a, 3b, 3c: Adhesive layer 4a, 4b: Release sheet 5, 5a, 5b: Protective layer S1, S2, S3, S4: Gas barrier adhesive sheet 31: Substrate 32: gas barrier layer 33: first electrode 34: organic EL layer 35: second electrode 36: inorganic sealing layer 37: adhesive layer 38: gas barrier layer 39: protective layer

Claims (6)

A gas barrier pressure-sensitive adhesive sheet having a gas barrier layer and a pressure-sensitive adhesive layer on a substrate,
In the gas barrier layer, a mixed region containing a non-transition metal M1 (silicon (Si 2 )) and a transition metal M2 (niobium (Nb) or tantalum (Ta)) is continuous at least in the thickness direction. A gas barrier, wherein at least a part of the mixed region satisfies the following relational expression (2) when the composition of the mixed region is represented by the following chemical composition formula (1): Adhesive sheet.
Chemical composition formula _{(1) :( M1) (M2} ) x O y N z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Wherein, M1: non-transition metal (silicon (Si 2 )) , M2: transition metal (niobium (Nb) or tantalum (Ta)), O: oxygen, N: nitrogen, x, y, z: stoichiometry Coefficient, a: maximum valence of M1, b: maximum valence of M2. The expression on the left side of relational expression (2) is an index of oxygen deficiency.)   The gas barrier layer is provided between the region A which is a region containing the transition metal M2 as the main component of the metal and the region B which is a region containing the non-transition metal M1 as the main component of the metal. The gas-barrier pressure-sensitive adhesive sheet according to claim 1, having a region. The gas barrier pressure-sensitive adhesive sheet according to claim 1 or 2 , wherein the transition metal M2 is niobium (Nb). The size of the oxygen vacancies of the indices of the formula of the left side of the equation (2) is, of claims 1, characterized in that in the range of 0.60 to 0.88 to claim 3 The gas-barrier pressure-sensitive adhesive sheet according to any one of the preceding claims. An electronic device comprising the gas-barrier pressure-sensitive adhesive sheet according to any one of claims 1 to 4 . The electronic device according to claim 5 , further comprising an organic electroluminescence element.

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