JP2019010731A - Gas barrier film and electronic device - Google Patents

Abstract

To provide a gas barrier film which is thin but has excellent gas barrier performance and flexibility and an electronic device having the gas barrier film.SOLUTION: There is provided a gas barrier film 1 having a gas barrier layer 3 on a substrate 2, wherein the gas barrier layer 3 has a mixed region containing a non-transition metal M1 and a transition metal M2 at least in the thickness direction, the value of a ratio of the atomic number ratio of the transition metal M2 to the atomic number ratio of the non-transition metal M1 measured by an X-ray photoelectron spectroscopic method is in the range of 0.02 to 49 in the thickness direction of the gas barrier layer 3, the region within the range has a layer thickness of 3 nm or more continuously in the thickness direction of the gas barrier layer 3 and the gas barrier layer 3 has a layer thickness in the range of 5 to 1000 nm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film and an electronic device. Specifically, the present invention relates to a gas barrier film having high gas barrier performance even when thin and excellent in flex resistance, and an electronic device including the gas barrier film.

  Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or film has been altered by various gases such as water vapor and oxygen. In order to prevent this, it is used in applications for packaging articles that require shutoff of various gases.

  In addition to the packaging applications described above, in order to prevent alteration due to various gases, it is used for sealing electronic devices such as solar cells, liquid crystal display elements, organic electroluminescence elements (hereinafter also referred to as organic EL elements). Has also been used.

  As a conventional gas barrier film, a film having a gas barrier layer formed on a substrate such as a film by a plasma chemical vapor deposition method (hereinafter also referred to as a plasma CVD method (CVD: Chemical Vapor Deposition)). Further, those having a gas barrier layer formed by applying a modification treatment after applying a coating liquid containing polysilazane as a main component on a substrate, or those using them in combination are known (for example, Patent Documents). 1-3.)

By the way, in recent years, it is used in electronic devices that require extremely high gas barrier properties, and a gas barrier layer is formed on a bendable substrate surface. Gas barrier films having excellent properties are demanded.
However, in the conventional gas barrier film described above, in order to obtain sufficient gas barrier performance that satisfies these requirements, the gas barrier layer must be formed to be a dense and thick layer, and as a result, When the gas barrier film is bent, there are problems such as cracking and a marked decrease in gas barrier performance.

JP 2009-255040 A Japanese Patent No. 3511325 JP 2012-106421 A

  The present invention has been made in view of the above problems and circumstances, and the solution to the problem is that the present invention provides a gas barrier film excellent in gas barrier performance and flex resistance even if it is thin, and the gas barrier. It is providing the electronic device which comprises a conductive film.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, the gas barrier film having a mixed region containing a transition metal and a non-transition metal in the gas barrier layer is very thin. In addition, the present inventors have found that a high gas barrier property can be obtained and excellent in bending resistance, and have led to the present invention.
That is, the said subject which concerns on this invention is solved by the following means.

1. A gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer has a mixed region containing a non-transition metal M1 and a transition metal M2 at least in a thickness direction;
In the mixed region, the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 0. The range of 02 to 49, and the region within the range is a layer thickness of 3 nm or more continuously in the thickness direction of the gas barrier layer,
A gas barrier film, wherein the gas barrier layer has a thickness of 5 to 1000 nm.

2. The gas barrier layer includes, in the thickness direction, an A region containing the transition metal M2, a B region containing the non-transition metal M1, and the mixed region.
In the region A, the atomic ratio of the transition metal M2 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 5 atom% or more,
2. The B region according to claim 1, wherein the atomic ratio of the non-transition metal M <b> 1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 5 atom% or more. Gas barrier film.

  3. The gas barrier film according to item 2, wherein the layer thickness of the region A is in the range of 3 to 100 nm.

  4). The gas barrier film according to any one of Items 1 to 3, wherein the non-transition metal M1 is silicon (Si).

  5. The gas barrier film according to any one of Items 1 to 4, wherein the transition metal M2 is a Group 5 element of a long-period periodic table.

  6). The gas barrier film according to any one of Items 1 to 5, wherein the transition metal M2 is niobium (Nb) or tantalum (Ta).

  7). The gas barrier film according to any one of claims 1 to 6, wherein oxygen is further contained in the composition of the mixed region.

8). The gas barrier film as set forth in claim 7, wherein 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 formula (2). .
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, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, 0.02 ≦ x ≦ 49, 0 <y, 0 ≦ z A: maximum valence of M1, b: maximum valence of M2.

  9. An electronic device comprising the gas barrier film according to any one of items 1 to 8.

  10. Item 10. The electronic device according to Item 9, which has a quantum dot-containing layer.

  11. 10. An electronic device according to item 9, comprising an organic electroluminescence element.

By the above means of the present invention, it is possible to provide a gas barrier film excellent in gas barrier performance and excellent in bending resistance even if it is thin, and an electronic device including the gas barrier film.
The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

According to the study by the present inventors, an oxygen-deficient composition film containing a non-transition metal (M1) compound (for example, an oxide) is used alone to form a sealing layer, or a transition metal (M2) When a sealing layer is formed using an oxygen-deficient composition film of a compound (for example, an oxide) alone, a tendency to improve the gas barrier property as the degree of oxygen deficiency increases is observed, but a remarkable gas barrier It did not lead to improvement of sex.
In response to this result, a single composition layer containing a compound (for example, oxide) whose main component is a non-transition metal (M1) and a compound (for example, oxide) whose main component is a transition metal (M2) A mixed region containing a composite oxide of a non-transition metal (M1) and a transition metal (M2) is formed, and the composite composition region has an oxygen deficiency composition. It has been found that the gas barrier property is remarkably improved as the size increases. As described above, this is because electronic bonds (interactions) between the non-transition metal (M1) and the transition metal (M2) rather than the bond between the non-transition metal (M1) and the bond between the transition metal (M2). It is estimated that the formation of oxygen vacancies in the mixed region forms a high-density structure in the mixed region and exhibits high gas barrier properties.

FIG. 2 shows the result of composition analysis by the X-ray Photoelectron Spectroscopy (XPS) performed by the inventors on an example of a gas barrier layer having a mixed region according to the present invention. Note that FIG. 2 shows silicon (Si), niobium (Nb), oxygen (O), and nitrogen (in the gas barrier layer when silicon (Si) is used as the non-transition metal and niobium (Nb) is used as the transition metal. It is an example which analyzed the atomic composition of N). In addition, the horizontal axis represents the depth in the thickness direction (sputter depth) from the surface of the gas barrier layer opposite to the substrate, and the vertical axis represents the atomic ratio (unit: atom%). .
As shown in FIG. 2, the gas barrier layer according to the present invention has a mixed region (C in FIG. 2) containing a non-transition metal and a transition metal. In the mixed region, a non-transition metal and a transition metal bond are generated rather than a non-transition metal bond or a transition metal bond, and the density of each atom in the network is increased, and a dense structure is formed. It is assumed that high gas barrier properties were obtained.
Further, as a result of the study by the present inventors, the mixed region can exhibit high gas barrier performance if it has a thickness of at least about 3 nm. Was also found to have high gas barrier performance. Thus, since the gas barrier film of the present invention can make the gas barrier layer very thin with high gas barrier performance, it is possible to obtain a gas barrier film having excellent bending resistance.

  Furthermore, in the mixed region shown in FIG. 2, it can be seen that the atomic ratio of the non-transition metal and the transition metal gradually changes. As a result, the stress in the gas barrier layer is not concentrated at one point at the time of bending or expansion / contraction, and the effect of stress relaxation can be obtained. Therefore, excellent bending resistance that cannot be obtained with conventional gas barrier films can be obtained. Inferred to have.

Sectional drawing which shows the structure of the gas barrier film of embodiment of this invention Graph showing the ratio of the number of atoms to the depth in the thickness direction of the gas barrier layer Sectional drawing which shows an example of a structure of the organic EL element which is embodiment of the electronic device of this invention Schematic sectional view showing an example of a vacuum ultraviolet ray irradiation apparatus applicable to formation of the B region constituting the gas barrier layer Top view of an evaluation device manufactured in the example

  The gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a substrate, and the gas barrier layer contains a non-transition metal M1 and a transition metal M2 at least in the thickness direction. The mixed region has a ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer. Is within a range of 0.02 to 49, and a region within the range is continuously 3 nm or more in the thickness direction of the gas barrier layer, and the thickness of the gas barrier layer is 5 It is characterized by being within a range of ˜1000 nm. This feature is a technical feature common to the claimed invention.

  As an embodiment of the present invention, from the viewpoint of obtaining excellent gas barrier properties and bending resistance, the gas barrier layer comprises an A region containing the transition metal M2 in the thickness direction and the non-transition metal M1. The region B contains and the mixed region, and the region A has an atomic ratio of the transition metal M2 measured by X-ray photoelectron spectroscopy of 5 atom% or more in the thickness direction of the gas barrier layer. In the B region, the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is preferably 5 atom% or more.

  As an embodiment of the present invention, the layer thickness of the region A is preferably in the range of 3 to 100 nm from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.

  As an embodiment of the present invention, the non-transition metal M1 is preferably silicon (Si) from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.

  As an embodiment of the present invention, it is preferable that the transition metal M2 is a Group 5 element in the long-period periodic table from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.

  In an embodiment of the present invention, the transition metal M2 is preferably niobium (Nb) or tantalum (Ta) from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.

  As an embodiment of the present invention, from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance, it is preferable that oxygen is further contained in the composition of the mixed region.

  As an embodiment of the present invention, from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance, when the composition of the mixed region is represented by the chemical composition formula (1), at least a part of the mixed region is used. Preferably satisfies the relational expression (2).

  The gas barrier film of the present invention can be suitably provided in an electronic device. The electronic device preferably has a quantum dot-containing layer. The electronic device preferably includes an organic electroluminescence element.

  Hereinafter, the present invention, its components, and modes for carrying out the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Outline of gas barrier film]
The gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a substrate, and the gas barrier layer contains a non-transition metal M1 and a transition metal M2 at least in the thickness direction. The mixed region has a value of the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer. Within the range of 0.02 to 49, and the region within the range is continuously 3 nm or more in the thickness direction of the gas barrier layer, and the layer thickness of the gas barrier layer is within the range of 5 to 1000 nm. It is characterized by being.
In the gas barrier film of the present invention, the entire gas barrier layer may be a mixed region.

When the gas barrier property of the gas barrier layer according to the present invention is calculated using a gas barrier film in which the gas barrier layer is formed on a substrate, the oxygen permeability measured by a method based on JIS K 7126-1987. Water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%, measured by a method according to JIS K 7129-1992, 1 × 10 ⁻³ ml / m ² · 24 h · atm or less. RH) is preferably a high gas barrier property of 1 × 10 ⁻³ g / m ² · 24 h or less.

  As an embodiment of the present invention, from the viewpoint of obtaining excellent gas barrier properties and bending resistance, the gas barrier layer contains an A region containing a transition metal M2 and a non-transition metal M1 in the thickness direction. It is preferable to have a B region and a mixed region. Details of each region will be described later.

FIG. 1 shows a cross-sectional configuration of a gas barrier film 1 according to an embodiment of the present invention. The gas barrier film 1 includes a gas barrier layer 3 on a substrate 2.
FIG. 1 shows an example in which the gas barrier layer 3 is provided only on one surface of the substrate 2, but the gas barrier layer 3 can be provided on both surfaces of the substrate 2 or on one surface. A plurality of gas barrier layers 3 may be provided.

  Hereinafter, although each area | region (A area | region, B area | region, and mixing area | region) etc. of the base material and gas barrier layer which comprise the gas barrier film of this invention is demonstrated in detail, the definition of the technical term used by the following description Will be described in advance.

In the present invention, the “region” means that the gas barrier layer is constant or arbitrary on a plane perpendicular to the thickness direction (stacking direction) of the gas barrier layer (that is, a plane parallel to the outermost surface of the gas barrier layer). A three-dimensional range (region) between two opposing surfaces formed when divided by a thickness of the same, and even if the composition of components in the region is constant in the thickness direction, gradually It may change to.
Regarding the A region, the B region, the mixed region, and the gas barrier layer, the “layer thickness” means the thickness of the gas barrier layer in the thickness direction. Further, the “layer thickness” in the present invention represents the sputter depth in XPS analysis in terms of SiO ₂ . The “layer thickness” of the gas barrier layer is from the outermost surface side of the gas barrier layer to the interface with the base material, and the “interface with the base material” refers to the gas barrier layer in the composition analysis by XPS described later. It was set as the position which becomes the intersection of the distribution curve of the main component element and the distribution curve of the main component element of the base material.
“Constituent” means a compound constituting a specific region of the gas barrier layer and a simple substance of metal or nonmetal.
The “mixture” refers to a product in a state where the constituent components of the A region and the B region 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 “composite oxide” refers to a compound (oxide) formed by chemically bonding the constituent components of the A region and the B region. 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 formed by physically combining the constituent components of the A region and the B region with each other by intermolecular interaction is also included in the “composite oxide” according to the present invention. And

<Base material>
As a base material used for this invention, the film or sheet | seat which consists of colorless and transparent resin is mentioned. 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; polyamide Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Cellulose ester resin.
Among these resins, resins selected from polyester resins, polyimide resins, cyclopolyolefin resins, and polycarbonate resins are particularly preferable. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

The thickness of the base material can be appropriately set in consideration of stability when 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 conveyed even in a vacuum.
Further, when the gas barrier layer according to the present invention is formed by plasma CVD, 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. It is more preferable, and it is especially preferable that it is the range of 50-100 micrometers.
Moreover, it is preferable to perform the surface activation process for cleaning the surface of a base material from a viewpoint of adhesiveness with the gas barrier layer mentioned later to the said base material. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

<A area>
The A region contains a transition metal (M2) or a compound containing a transition metal (M2) (for example, a transition metal oxide or the like), and the X-ray photoelectron spectroscopy described later in the thickness direction of the gas barrier layer. This is a region where the atomic ratio of the transition metal (M2) measured by 1 is 5 atom% or more.
The thickness of the A region is preferably in the range of 3 to 100 nm in the thickness direction of the gas barrier layer from the viewpoint of achieving both gas barrier properties and optical characteristics, and in the range of 4 to 25 nm. It is more preferable that it is in the range of 5 to 15 nm.

The transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.
Among these, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, etc. are mentioned as a transition metal (M2) from which a favorable gas barrier property is obtained. Among these, Nb, Ta, and V, which are Group 5 elements, are considered to be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer. be able to.

  In particular, when the transition metal (M2) is a Group 5 element (particularly Nb) and the non-transition metal (M1) described later is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

<B area>
The B region contains a non-transition metal (M1) or a compound containing a non-transition metal (M1) (for example, a non-transition metal oxide or the like). In the thickness direction of the gas barrier layer, the X-ray described later This is a region where the atomic ratio of the non-transition metal (M1) measured by photoelectron spectroscopy is 5 atom% or more.
The thickness of the region B is preferably in the range of 10 to 1000 nm in the thickness direction of the gas barrier layer, preferably in the range of 20 to 500 nm, from the viewpoint of achieving both gas barrier properties and productivity. More preferably, it is more preferably in the range of 50 to 300 nm.

  As the non-transition metal (M1), a non-transition metal selected from metals of Groups 12 to 14 of the long-period periodic table is preferable. The non-transition metal (M1) is not particularly limited, and any metal of Group 12 to Group 14 can be used alone or in combination. For example, Si, Al, Zn, In, Sn, and the like can be used. Can be mentioned. Especially, it is preferable that Si, Sn, or Zn is included as the non-transition metal (M1), Si is more preferable, and Si alone is particularly preferable.

<Mixed area>
The mixed region contains a non-transition metal (M1) and a transition metal (M2) or a compound containing them, and the non-transition metal measured by X-ray photoelectron spectroscopy described later in the thickness direction of the gas barrier layer. The ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the transition metal M1 is within a range of 0.02 to 49, and a region within the range is continuously in the thickness direction of the gas barrier layer. This is a region having a layer thickness of 3 nm or more. The mixed region may have a region at least a part of which overlaps with the A region or the B region.

  Here, the mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed. .

  The region other than the mixed region of the gas barrier layer may be a region such as a non-transition metal (M1) oxide, nitride, oxynitride, or oxycarbide, or a transition metal (M2) oxide. It may be a region of nitride, oxynitride, oxycarbide, or the like.

(Oxygen deficient composition)
In the present invention, it is preferable that oxygen is contained in the composition of the mixed region, and further, a non-stoichiometric composition (oxygen-deficient composition) in which a part of the composition contained in the mixed region is deficient in oxygen. It is preferable that
In the present invention, the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition. In addition, 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, M1 represents a non-transition metal, M2 represents a transition metal, O represents oxygen, N represents nitrogen, and x, y, and z represent stoichiometric coefficients, respectively. a represents the maximum valence of M1, and b represents the maximum valence of M2.
Hereinafter, when no special distinction is required, 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 of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) _x O _y N _z which is the formula (1). As is clear from this composition, the composition of the composite region may partially include a nitride structure, and it is more preferable from the viewpoint of barrier properties to include a nitride structure.
Here, the maximum valence of the non-transition metal (M1) is a, the maximum valence of the transition metal (M2) is b, the valence of O is 2, and the valence of N is 3. When the composition of the composite region (including a part of the nitride) is a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N. In this case, non-transition metal (M1) And the transition metal (M2) are bonded to either O or N. In the present invention, when two or more kinds are used together as the non-transition metal (M1), or when two or more kinds are used together as the transition metal (M2), the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.

On the other hand, in the mixed region according to the present invention, when (2y + 3z) / (a + bx) <1.0 shown by the relational expression (2), a bond between 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, and such a state is the above-mentioned “oxygen deficiency”.
In the oxygen deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are 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 defined as a region where the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49 and the thickness is 3 nm or more. It is the same definition as that.
In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a mixed region that satisfies this condition exists with a thickness of a predetermined value or more (3 nm). Therefore, it is thought that it contributes to the improvement of gas barrier properties. In addition, since it is considered that the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2), the more the gas barrier property can be improved, the mixed region is a region satisfying 0.1 ≦ x ≦ 10. It is preferable to include a thickness of 3 nm or more, more preferably include a region satisfying 0.2 ≦ x ≦ 5 at a thickness of 3 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 to a thickness of 3 nm or more. It is further preferable to contain.

  Here, as described above, if there is a region satisfying 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 obtained. Although it was confirmed that the mixed region exhibits at least a part of the composition, (2y + 3z) / (a + bx) ≦ 0.9, and (2y + 3z) / (a + bx) ≦ 0.85 in the mixed region. It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill (2y + 3z) / (a + bx) <= 0.8. Here, the smaller the value of (2y + 3z) / (a + bx) in the mixed region, the higher the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and it is further preferable that 0.4 ≦ (2y + 3z) / (a + bx).

In the present invention, the thickness of the mixed region where good gas barrier properties can be obtained is 3 nm or more as the sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and this thickness is 5 nm or more. Is preferably 10 nm or more, more preferably 20 nm or more. The thickness of the mixed region is not particularly limited 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.
A gas barrier layer having a mixed region having a specific configuration as described above exhibits 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 each region)
The composition distribution in the A region, the B region, and the mixed region according to the present invention, the thickness of each region, and the like should be measured by X-ray photoelectron spectroscopy (abbreviation: XPS) described in detail below. It can ask for.

  Specifically, 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 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), carbon (C) element concentration, etc. can be measured by combining X-ray photoelectron spectroscopy measurement with rare gas ion sputtering such as argon. It can be created by sequentially performing surface composition analysis while exposing the interior from the surface of the barrier layer.

A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time). In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally 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 the XPS depth profile measurement Can be adopted. In addition, as a sputtering method employed for such XPS depth profile measurement, 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 preferable to set to sec (SiO ₂ thermal oxide film conversion value).

An example of specific conditions of XPS analysis applicable to the composition analysis of the gas barrier layer according to the present invention is shown below.
・ Analyzer: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval is 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background is obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI. 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 obtained data, the composition ratio is calculated, the non-transition metal (M1) and the transition metal (M2) coexist, and the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 A range in which the value is 0.02 to 49 is obtained. And the area | region where the area | region in the said range is 3 nm or more of layer thickness continuously in the thickness direction of a gas barrier layer is defined as a "mixed area | region," and the thickness is calculated | required. The thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO ₂ .
In the present invention, the thickness of the mixed region has no upper limit of the thickness in the mixed region from the viewpoint of gas barrier properties, but is preferably in the range of 3 to 100 nm, more preferably from the viewpoint of optical properties. Is in the range of 5 to 50 nm, more preferably in the range of 10 to 30 nm.

Below, an example of the gas barrier layer which has the mixing area | region which concerns on this invention is demonstrated using FIG.
FIG. 2 is a graph showing the atomic ratio in the thickness direction of the gas barrier layer. Silicon in the gas barrier layer when silicon (Si) is used as the non-transition metal and niobium (Nb) is used as the transition metal. This is an example of analyzing the atomic composition of (Si), niobium (Nb), oxygen (O), nitrogen (N), and carbon (C). In addition, the horizontal axis represents the depth in the thickness direction (sputter depth) from the surface of the gas barrier layer opposite to the substrate, and the vertical axis represents the atomic ratio (unit: atom%). . Carbon was omitted because almost no carbon was detected. Moreover, the arrow described on the graph has shown each position of A area | region, B area | region, a mixing area | region (C), and a gas barrier layer (3) in the thickness direction of a gas barrier layer.

<Method for forming each region>
(Formation of area A)
The A region of the present invention can be produced by forming a region containing a transition metal (M2) described below.

  Examples of the transition metal (M2) according to the present invention include Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like from the viewpoint of obtaining good gas barrier properties as described above. In particular, Nb, Ta, and V, which are Group 5 elements, can be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer.

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

  These vapor phase film forming methods can be used by known methods. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. In particular, it is possible to form a film without damaging the functional element, and since it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method, and more preferably formed by a sputtering method. preferable.

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

  A reactive sputtering method using a transition mode that 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 Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, oxynitrides, oxycarbides, etc. are formed. can do. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.

  The sputtering method may be a multi-source simultaneous sputtering method using a plurality of sputtering targets including a single transition metal (M2) or an oxide thereof. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The methods and conditions described in JP 2013-047361 A can be referred to as appropriate.

  The film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the gas concentration during the film forming. Examples include one or more conditions selected from the group consisting of supply amount, degree of vacuum during film formation, and power during film formation. These film formation conditions (preferably oxygen partial pressure) are By adjusting, a mixed region made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions. According to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area | region.

(Method for forming region B)
The B region of the present invention can be produced by forming a region containing a non-transition metal (M1) described below.
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 deposition method can be used by a known method. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. In particular, it is possible to form a film without damaging the functional element, and since it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method. A non-transition metal is formed by a sputtering method. It can be used as a target.

  As another method, a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal is also a preferable method.

In the present invention, “polysilazane” applicable to formation of the B region is a polymer having a silicon-nitrogen bond in the structure, and includes SiO ₂ , Si _{3 made of} Si—N, Si—H, N—H, 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 using polysilazane so as not to impair the planarity of the above-described base material, as described in JP-A-8-112879, Polysilazanes that can be modified to silicon oxide, silicon nitride, or silicon oxynitride at low temperatures are preferred.
Examples of such polysilazane include compounds having a structure represented by the following general formula (1).

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 preferred from the viewpoint of the denseness of the B region constituting the resulting 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, so that the adhesion to an adjacent substrate is improved and it may be hard. The ceramic film made of polysilazane can be tough, and even when the layer thickness is increased, the generation of cracks is preferred.

These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6- or 8-membered ring coexist.

The molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), 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 commercially available products can be used as they are as coating solutions containing polysilazane compounds.

  Other examples of polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially (Kaihei 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). No. 1), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (Japanese Patent Laid-Open No. 6-306329), metal fine 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, for example, paragraphs (0024) to (0040) of JP2013-255910A, paragraphs (0037) to (0043) of JP2013-188942A, JP Paragraphs (0014) to (0021) of JP2013-151123A, Paragraphs (0033) to (0045) of JP2013-052569A, Paragraphs (0062) to (0075) of JP2013-129557A. ), And the contents described in paragraphs (0037) to (0064) of JP2013-226758A can be applied.

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one 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, ethers such as aliphatic ethers and alicyclic ethers. it can. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, 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 liquid containing polysilazane is preferably about 0.2 to 35% by mass, although it varies depending on the layer thickness of the target gas barrier layer and the pot life of the coating liquid.

  In addition, an amine or a metal catalyst can be added to the coating liquid containing polysilazane in order to promote 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, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to. Moreover, these commercial items may be used independently and may be used in mixture of 2 or more types.

  In addition, in the coating liquid containing polysilazane, the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable.

  In addition to polysilazane, the coating liquid containing polysilazane can contain an inorganic precursor compound. The inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared. For example, compounds other than polysilazane described in paragraphs “0110” to “0114” of JP2011-143577A can be appropriately employed.

An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane. By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the coating composition can be changed to a stable composition close to SiO ₂ after drying. 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), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.
In particular, Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.

Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum trisec-butyrate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), 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 Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxy aluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.), etc. It is possible.
In addition, when using these compounds, it is preferable to mix with the coating liquid containing polysilazane in inert gas atmosphere. This is to prevent these compounds from reacting with moisture and oxygen in the atmosphere and causing intense oxidation. Moreover, when mixing these compounds and polysilazane, it is preferable to heat up to 30-100 degreeC, and to hold | maintain for 1 minute-24 hours, stirring.

  The content of the additive metal element in the polysilazane-containing layer constituting the gas barrier film according to the present invention is preferably in the range of 0.05 to 10 mol% with respect to 100 mol% of silicon (Si). More preferably, it exists in the range of 0.5-5 mol%.

In the formation of the B region using polysilazane, it is preferable to perform a modification treatment after forming the polysilazane-containing layer.
The modification treatment is a treatment in which polysilazane is imparted with energy and part or all thereof is converted into silicon oxide or silicon oxynitride.

  For the modification treatment in the present invention, a known method based on the conversion reaction of polysilazane can be selected, and examples thereof include known plasma treatment, plasma ion implantation treatment, ultraviolet irradiation treatment, vacuum ultraviolet irradiation treatment and the like. In the present invention, a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a low temperature is preferable. Conventionally known methods can be used for plasma and ozone. In the present invention, a gas barrier layer is formed by providing a coating film of a polysilazane-containing coating liquid of a coating method on a substrate and applying a vacuum ultraviolet irradiation treatment in which a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less is irradiated to perform a modification treatment. The forming method is preferred.

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

  The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in polysilazane, and the bonding of atoms is an action of only a photon called a photon process. Thus, a silicon oxide film or a silicon oxynitride film is formed at a relatively low temperature (about 200 ° C. or lower) by proceeding an oxidation reaction with active oxygen or ozone while directly cutting.

  For details of these reforming treatments, for example, paragraphs (0055) to (0091) of JP2012-086394A, paragraphs (0049) to (0085) of JP2012-006154A, JP The contents described in paragraphs (0046) to (0074) of 2011-251460 can be referred to.

(Method for forming mixed region)
As a mixed region forming method, as described above, when forming the A region and the B region, it is preferable to appropriately adjust each formation condition to form the mixed region in the gas barrier layer.

When the B region is formed by the above-described vapor deposition method, for example, the ratio of the non-transition metal (M1) and oxygen in the deposition raw material, the ratio of the inert gas and the reactive gas during the deposition, Mixing 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 Regions can be formed.
When forming the B region by the above-described coating film forming method, for example, a film forming raw material type (polysilazane type or the like) 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.

In the case where the A region is formed by the above-described vapor deposition method, for example, the ratio of the transition metal (M2) and oxygen in the deposition material, the ratio of the inert gas and the reactive gas during the deposition, A mixed region 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 Can be formed.
Note that, in order to control the thickness of the mixed region by the above-described method, the formation conditions of the method of forming the A region and the B region can be adjusted as appropriate. For example, when forming the A region by a vapor deposition method, a desired thickness can be obtained by controlling the deposition time.
In addition to this, a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.

As a method for directly forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2). One-way sputtering using a composite target made of an oxide as a sputtering target may be used.
In addition, the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The description of 2013-043761 gazette etc. can be referred suitably.

  The film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming process. One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content) By adjusting the pressure, a thin film made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area | region.

<Other functional layers>
In the gas barrier film of the present invention, in addition to the constituent layers described above, other functional layers can be provided as long as the object effects of the present invention are not impaired.

(Anchor coat layer)
An anchor coat layer may be disposed on the surface of the base material on the side where the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion between the base material and the gas barrier layer.

  As anchor coating agents used for the anchor coat layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

  The anchor coat layer can also be formed by a vapor deposition method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Further, by forming an anchor coat layer as described in JP-A-2004-314626, when an inorganic thin film is formed thereon by a vapor deposition method, a gas generated from the substrate side is generated. An anchor coat layer can also be formed for the purpose of blocking to some extent and controlling the composition of the inorganic thin film.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Hard coat layer)
A hard coat layer may be disposed on the surface (one side or both sides) of the substrate. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. A layer containing a cured product of the functional resin, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. You may use the commercially available base material in which the hard-coat layer is formed previously.

  The thickness of the hard coat layer is preferably in the range of 0.1 to 15 μm, and more preferably in the range of 1 to 5 μm, from the viewpoint of smoothness and bending resistance.

  Examples of the active energy ray-curable resin applicable to the hard coat layer forming material include a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, and a mercapto compound having an acrylate compound and a thiol group. Examples thereof include resin compositions, resin compositions in which polyfunctional acrylate monomers such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicone resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples thereof include a thermosetting urethane resin composed of a coat, an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

  The method for forming the hard coat layer is not particularly limited, but it is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the hard coat layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described active energy ray-curable resin as necessary. In addition, regardless of the position of the hard coat layer, any hard coat layer may use an appropriate resin or additive for improving the film formability and preventing the generation of pinholes in the film.

  The thickness of the hard coat layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. It is preferable.

[Electronic device]
The gas barrier film of the present invention can be preferably applied to an electronic device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.

  Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, a QD film having a quantum dot (QD) -containing resin layer, an organic electroluminescence element (organic EL element), and a liquid crystal display. An element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like can be given. 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) film>
The gas barrier film of the present invention can be applied to a QD film containing quantum dots (QD).

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

<Quantum dots>
In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases 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) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to 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 US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155 Can be mentioned.

  The QD is generated 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, BeS, 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 be preferably used.

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

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

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

<Organic EL device>
An organic EL element which is a representative example of an electronic device to which the gas barrier film of the present invention is applied includes, for example, a pair of electrodes 20 and an organic functional layer 30 positioned between the pair of electrodes 20 on the transparent substrate 10. And a sealing material 40 that covers the organic functional layer 30. The transparent substrate 10 includes the gas barrier film 1 of the present invention.

The organic functional layer 30 includes at least a light emitting layer, and includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like as necessary.
The light-emitting layer contains a light-emitting organic compound, and holes injected directly from one electrode 20 (anode) or injected from the anode through a hole transport layer and the like, and the other electrode 20 (cathode) ) Or electrons injected directly through the electron transport layer or the like are recombined to emit light.

  The organic functional layer 30 and the electrode 20 are likely to be deteriorated by the intrusion of gas such as oxygen and water in the atmosphere. In order to suppress a decrease in light emission performance due to such deterioration of the organic functional layer 30 or the like, the organic EL element G includes the above-described gas barrier film 1 as the substrate 10, but the gas barrier property as the sealing material 40. A film 1 can also be provided.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
<< Production of gas barrier film >>
Gas barrier films 1 to 19 were produced according to the following method.

[Preparation of gas barrier film 1]
<Preparation of base material>
Clear hard coat layer 1 (back side) and clear hard coat layer 2 on both sides of a 100 μm thick polyethylene terephthalate film (Lumirror (registered trademark) U48, abbreviated as PET film) manufactured by Toray Industries, Inc. (Gas barrier layer forming surface side) was formed by the following method.

(Formation of clear hard coat layer)
A UV curable resin (manufactured by Aika Industry Co., Ltd., product number: Z731L) is applied to the back side of the PET film (the side opposite to the side on which the gas barrier layer is formed) so that the dry layer thickness is 0.5 μm. After coating by the wet coating method, the formed coating film is dried at 80 ° C., and then cured in air using a high-pressure mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm ² to clear the back side. Hard coat layer 1 was formed.

Next, using UV curable resin “OPSTAR (registered trademark) Z7527” manufactured by JSR Corporation on the surface side of the PET film (surface on which the gas barrier layer is formed), wet coating so that the dry layer thickness is 2 μm. After coating by the method, it is dried at 80 ° C., and then cured under a condition of irradiation energy of 0.5 J / cm ² using a high-pressure mercury lamp in the air, and a clear hard coat layer having a thickness of 2 μm on the surface side. 2 was formed.

<Formation of gas barrier layer 1>
(Formation of region containing non-transition metal (M1))
A non-transition metal (M1) constituting a gas barrier layer is contained on the surface side of the substrate on which the clear hard coat layer 2 is formed by a vapor phase method / sputtering (magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100). A region was formed. The sputtering apparatus used is capable of two-way simultaneous sputtering.

Here, a polycrystalline Si target was used as a target, and a mixed gas of Ar and O ₂ was used as a process gas, so that the layer thickness was 900 nm by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Film formation was performed by adjusting the oxygen partial pressure so that the composition was SiO ₂ . In addition, film formation using a glass substrate is performed in advance, and the condition of the composition is determined by adjusting the oxygen partial pressure. The condition where the composition near the depth of 10 nm from the surface layer becomes SiO ₂ is found, and the condition is applied. did. In addition, regarding the layer thickness, after taking the data of the change in the layer thickness with respect to the film formation time in the range of 100 to 300 nm and calculating the layer thickness formed per unit time, the film formation time is set to the set layer thickness. The layer thickness was adjusted by setting.

By the method described above on one surface of the substrate, the composition is a layer which is SiO ₂ is a non-transition metal oxide was formed at a layer thickness of 900 nm.

(Formation of region containing transition metal (M2))
On the region containing the non-transition metal (M1) formed above, a region containing the transition metal (M2) was formed by a vapor phase method / sputtering (a magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100).

As a target, a commercially available oxygen-deficient niobium oxide target (composition: Nb ₁₂ O ₂₉ ) was used, a mixed gas of Ar and O ₂ was used as a process gas, a magnetron sputtering apparatus, DC sputtering, and a layer thickness of 100 nm. The film was formed as follows. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was 12% under the film forming conditions. It should be noted that, by film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time is obtained under the film formation conditions, and after calculating the layer thickness formed per unit time, the set layer thickness is obtained. The film formation time was set as follows.
Thus, a gas barrier layer having a layer thickness of 1000 nm was formed.

(Measurement of layer thickness of A region, B region and mixed region)
In the gas barrier layer (layer thickness 1000 nm) formed by the above method, the layer thicknesses of the A region, the B region, and the mixed region were measured.
The composition distribution profile in the thickness direction was measured on the surface side of the gas barrier layer 1 by XPS analysis. The XPS analysis conditions are as follows. The sample used for the analysis was a sample stored in an environment of 20 ° C. and 50% RH after sample preparation.

<XPS analysis conditions>
・ Device: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements are Si (non-transition metal M1), Nb (transition metal M2), O, N, and C.

From the obtained data, in the thickness direction of the gas barrier layer, (1) the region where the atomic ratio of Nb (transition metal M2) is 5 atom% or more is the A region, and (2) Si (non-transition metal M1). A region having an atomic ratio of 5 atom% or more is a B region, and (3) the ratio of the atomic ratio of Si (non-transition metal M1) to the atomic ratio of Nb (transition metal M2) is 0.02 to 49. The region where the layer thickness within the range is 3 nm or more was defined as a mixed region, and the layer thickness of each region was measured. The layer thickness represents the sputter depth in XPS analysis in terms of SiO ₂ .

(Calculation of oxygen deficiency index (2y + 3z) / (a + bx) in mixed region)
The value of (2y + 3z) / (a + bx) in the thickness direction in the mixed region was calculated. Here, a is the maximum valence 4 of Si (M1), and b is the maximum valence 5 of Nb (M2). Further, x, y, and z are values of the atomic ratios of M2, O, and N when the atomic ratio of M1 is 1, which is obtained from XPS analysis. Then, the minimum value of (2y + 3z) / (a + bx) in the mixed region was obtained as an oxygen deficiency index, and when the minimum value was less than 1.0, it was determined that the mixed region was in an oxygen deficient state.

[Production of Gas Barrier Films 2 to 10, 17 to 19]
In the production of the gas barrier film 1, by changing the type of non-transition metal (M1) and the type of transition metal (M2) to the types shown in Table 1, and adjusting the oxygen partial pressure and film formation time as appropriate The films were formed to have the layer thicknesses of the A region, the B region, and the mixed region described in Table 1. The gas barrier film 17 only formed a region containing the non-transition metal (M1), and did not form a region containing the transition metal (M2).
A commercially available metal Ta target was used as the Ta sputtering target, a commercially available metal V target was used as the V sputtering target, and a commercially available metal Al target was used as the Al sputtering target.

[Preparation of gas barrier film 11]
In the production of the gas barrier film 1, a gas barrier film 11 was produced in the same manner except that the formation method of the region containing the transition metal (M2) was changed from the sputtering method to the following coating method.

(Formation of region containing transition metal (M2))
On the region containing the non-transition metal (M1), Nb (n-OC ₃ H ₇ ) ₅ (manufactured by Kojundo Chemical Laboratory Co., Ltd.) is diluted with isopropanol to a solid content concentration of 5%. Prepared. Then, after coating the prepared coating liquid on the metal (M1) containing layer with a bar coater, drying was performed at 80 ° C. for 1 minute as a drying condition. Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment using an Xe excimer lamp with a wavelength of 172 nm under the conditions of an oxygen concentration of 0.1% by volume and an irradiation energy of 3.0 J / cm ² to obtain a thickness of 25 nm. The transition metal (M2) -containing layer was formed.

[Preparation of gas barrier films 12, 13]
In the production of the gas barrier film 1, the formation of the region containing the non-transition metal (M1) and the formation of the region containing the transition metal (M2) are performed using a polycrystalline Si target and an Nb target as targets, Is the same except that a region containing a non-transition metal (M1) and a transition metal metal (M2) is formed using Ar and O ₂ by performing a DC simultaneous sputtering dual sputtering. Thus, gas barrier films 12 and 13 were produced. The gas barrier layer was formed so that the gas barrier film 12 had a layer thickness of 100 nm and the gas barrier film 13 had a layer thickness of 20 nm.

[Production of gas barrier films 14 to 16]
In the production of the gas barrier film 1, the method of forming the region (SiO ₂ ) containing the non-transition metal (M1) is changed from a sputtering method to an excimer modification method using perhydropolysilazane (abbreviation: PHPS) described below. Gas barrier films 14 to 16 were produced in the same manner except that the film was formed by the above process.

<Formation of Region Containing Non-Transition Metal (M1): Excimer Modification Method Using PHPS>
A polysilazane containing Si was used as the non-transition metal (M1), and a non-transition metal (M1) -containing layer was formed by a coating / modification method. The coating conditions and the modification conditions are shown below.

(Application conditions)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials, NN120-20), and an amine catalyst (N, N, N, N′-tetramethyl-1,6-diaminohexane) (TMDAH)) and a 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) are mixed at a ratio of 4: 1 (mass ratio) to prepare a coating solution. did.

  Next, in a nitrogen atmosphere in the glove box, the coating solution is applied by spin coating so that the dry layer thickness is 230 nm, dried at 80 ° C. for 10 minutes, and a coating film containing a non-transition metal (M1) Formed. In the production of the gas barrier film 14, the dry layer thickness was formed to 230 nm in this way. Further, by adjusting the coating amount, the gas barrier film 15 was formed to have a dry layer thickness of 60 nm, and the gas barrier film 16 was formed to have a dry layer thickness of 10 nm.

(Reforming process with excimer)
Next, the sample on which the coating film containing the non-transition metal (M1) was formed was placed in the vacuum ultraviolet irradiation apparatus shown in FIG. 4 having the Xe excimer lamp with a wavelength of 172 nm, and the irradiation energy was 5.0 J / cm ² . Vacuum ultraviolet irradiation treatment was performed. At this time, nitrogen and oxygen were supplied into the chamber, and the oxygen concentration in the irradiation atmosphere was adjusted to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.

In the vacuum ultraviolet irradiation apparatus (100) shown in FIG. 4, reference numeral 101 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausts the gas from a gas discharge port (not shown). It is possible to substantially remove water vapor from the water and maintain the oxygen concentration at a predetermined concentration. Reference numeral 102 denotes an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm ² ) having a double tube structure that irradiates vacuum ultraviolet light of 172 nm, and reference numeral 103 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 104 denotes a sample stage. The sample stage 104 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 101 by a moving means (not shown). The sample stage 104 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 105 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm. Reference numeral 106 denotes a light-shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 2.

  The energy applied to the sample coating layer surface in the vacuum ultraviolet light irradiation step was measured using a 172 nm sensor head using a UV integrating light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is installed in the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 101 is vacuum ultraviolet light. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the irradiation step, and measurement was performed by moving the sample stage 104 at a speed of 0.5 m / min. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 102, an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.

Based on the irradiation energy obtained by this measurement, the moving speed of the sample stage was adjusted to adjust the irradiation energy amount to 5.0 J / cm ² . The vacuum ultraviolet irradiation was performed after aging for 10 minutes.

<Evaluation of gas barrier properties: Ca method evaluation>
According to the following measurement method, the water vapor permeability (gas barrier property) of each gas barrier film was evaluated.

  The Ca method evaluation sample (type evaluated by permeation concentration) prepared as described below was stored in an environment of 85 ° C. and 85% RH, and the corrosion rate of Ca was observed at regular intervals. After 1 hour, 5 hours, 10 hours, 20 hours, and after that, observation and transmission density measurement (average of 4 points) every 20 hours, when the measured transmission density is less than 50% of the initial value of transmission density The observation time was obtained and used as an index of gas barrier properties. When the transmission density measured by storage for 500 hours was 50% or more of the initial value of transmission density, it was set to 500 hours or more.

(Preparation of Ca evaluation sample)
After the surface of the gas barrier layer of the gas barrier film was UV washed, a thermosetting sheet-like adhesive (epoxy resin) as a sealing resin layer was bonded to the gas barrier layer surface with a thickness of 20 μm. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

  One side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned. Then, Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm. A glass plate on which Ca has been deposited is mounted in a glove box, and the sealing resin layer surface of the gas barrier film to which the sealing resin layer is bonded is placed in contact with the Ca deposition surface of the glass plate, and bonded by vacuum lamination. did. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.

The results obtained as described above were evaluated according to the following evaluation criteria. In the present invention, 3 or more was considered acceptable. The results are shown in Table 1.
5: 500 hours or more 4: 400 hours or more but less than 500 hours 3: 300 hours or more but less than 400 hours 2: 200 hours or more but less than 300 hours 1: less than 200 hours

<Evaluation of bending resistance>
As the bending treatment, each of the gas barrier films produced was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 8 mm. Thereafter, the water vapor permeability (gas barrier property) of the gas barrier film was evaluated by the same method as described above.
Then, regarding the observation time when the transmission density becomes less than 50% of the transmission density initial value, when the observation time T1 before bending and the observation time T2 after 100 times bending are taken, the results obtained by T2 / T1 are Evaluation was made according to the following evaluation criteria. In the present invention, 3 or more was considered acceptable. The results are shown in Table 1.

5: (T2 / T1) is 0.95 or more 4: (T2 / T1) is 0.90 or more and less than 0.95 3: (T2 / T1) is 0.85 or more and less than 0.90 2: ( T2 / T1) is 0.80 or more and less than 0.85 1: (T2 / T1) is less than 0.80

<Evaluation results>
As is apparent from the results shown in Table 1, it was found that the gas barrier film of the present invention has high gas barrier performance and excellent bending resistance even when it is thin. On the other hand, the gas barrier film of the comparative example was inferior in any item.
Moreover, since the gas barrier film 19 of the comparative example made the layer thickness of the gas barrier layer too thin, the value of the ratio of the atomic number ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 was 0.02 to 0.02. The region within the range of 49 could not be formed so as to have a layer thickness of 3 nm or more continuously in the thickness direction of the gas barrier layer, and a mixed region could not be formed.

Example 2
[Production of Evaluation Devices 1 to 16]
Using the gas barrier films 1 to 16 of the present invention, evaluation devices 1 to 16 were prepared, and it was evaluated whether the gas barrier film of the present invention could be used for an evaluation device. FIG. 5 shows the configuration of the evaluation device. The evaluation device can be obtained by forming a Ca vapor deposition layer 202, an electrode 203, an organic polymer layer 204, and a gas barrier layer 205 in this order on a substrate 201 as shown in FIG.

As the base material 201, an alkali-free glass plate having a thickness of 0.7 mm and a size of 50 mm × 50 mm was used.
The Ca vapor deposition layer 202 was UV-cleaned on one side of the substrate 201 and then vapor-deposited Ca in the center of the substrate 201 with a size of 14 mm × 20 mm using a mask. For vapor deposition, a vacuum vapor deposition apparatus manufactured by ALS Technology was used, and the thickness of the Ca vapor deposition layer 202 was set to 80 nm.

  The mask used for the Ca deposition was replaced with a mask having a pattern for forming the electrode 203, and aluminum was deposited to form an electrode 203 having a thickness of 200 nm. The size of the area | region of Ca vapor deposition layer 202 which is not coat | covered with the electrode 203 was 10 mm x 20 mm.

Next, the organic polymer layer 204 was formed by flash evaporation using a mixture of the following raw materials. The pressure at the time of flash vapor deposition was 3 Pa, and the conditions for the UV curing treatment were ² J / cm ² .
1,9-nonanediol diacrylate 75 parts by weight Trimethylolpropane triacrylate 14 parts by weight Phenoxyethyl acrylate 6 parts by weight 2,4,6-trimethylbenzophenone 5 parts by weight

  A mask was used to form the organic polymer layer 204, and the organic polymer layer 204 was formed in the center of the substrate 201 so as to have a size of 26 mm × 26 mm. In the range of 22 mm × 22 mm in the central portion covering the Ca vapor deposition layer 202, the thickness is 1 μm, and outside the range of the central portion 22 mm × 22 mm, the thickness gradually decreases. The thickness of the organic polymer layer 204 was adjusted.

(Gas barrier layer)
A gas barrier layer 205 having a size of 36 mm × 36 mm was formed in the center of the gas barrier layer substrate 201 as a gas barrier layer having the same composition as that of the gas barrier layer of the present invention produced in Example 1.

<Evaluation results>
The electrodes of each of the evaluation devices 1 to 16 were connected to an electrical resistance measuring device, and the initial resistance value (unit) between the electrodes was measured. While being connected to the measuring apparatus, each of the evaluation devices 1 to 16 was stored in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH, and a change in resistance value with time was measured. The time (h) when the resistance value was doubled from the initial resistance value was determined. The longer the time, the higher the gas barrier property. Here, it was found that the evaluation devices 1 to 16 using the gas barrier film of the present invention have high gas barrier properties and can be used for the evaluation device.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Base material 3 Gas barrier layer A A area B B area C Mixed area G Organic EL element 10 Transparent substrate 20 Electrode 30 Organic functional layer 40 Sealant 100 Vacuum ultraviolet irradiation apparatus 101 Apparatus chamber 102 Xe excimer lamp 103 Excimer lamp holder 104 Sample stage 105 Polysilazane compound coating layer forming sample 106 Light shielding plate

Claims (11)

A gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer has a mixed region containing a non-transition metal M1 and a transition metal M2 at least in a thickness direction;
In the mixed region, the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 0. The range of 02 to 49, and the region within the range is a layer thickness of 3 nm or more continuously in the thickness direction of the gas barrier layer,
A gas barrier film, wherein the gas barrier layer has a thickness of 5 to 1000 nm. The gas barrier layer includes, in the thickness direction, an A region containing the transition metal M2, a B region containing the non-transition metal M1, and the mixed region.
In the region A, the atomic ratio of the transition metal M2 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 5 atom% or more,
2. The B region according to claim 1, wherein the atomic ratio of the non-transition metal M <b> 1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 5 atom% or more. Gas barrier film.   The gas barrier film according to claim 2, wherein the layer thickness of the region A is in the range of 3 to 100 nm.   4. The gas barrier film according to claim 1, wherein the non-transition metal M <b> 1 is silicon (Si). 5.   The gas-barrier film according to any one of claims 1 to 4, wherein the transition metal M2 is a Group 5 element of a long-period periodic table.   The gas barrier film according to any one of claims 1 to 5, wherein the transition metal M2 is niobium (Nb) or tantalum (Ta).   The gas barrier film according to any one of claims 1 to 6, further comprising oxygen in the composition of the mixed region. The gas barrier film according to claim 7, wherein 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 formula (2). .
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, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, 0.02 ≦ x ≦ 49, 0 <y, 0 ≦ z A: maximum valence of M1, b: maximum valence of M2.   An electronic device comprising the gas barrier film according to any one of claims 1 to 8.   The electronic device according to claim 9, further comprising a quantum dot-containing layer.   The electronic device according to claim 9, further comprising an organic electroluminescence element.

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