TW201730009A - Gas barrier film, and electronic device provided with same - Google Patents

Abstract

The present invention addresses the problem of providing a gas barrier film which exhibits excellent productivity, while having high gas barrier properties. This gas barrier film (1) is characterized by having a gas barrier layer (3) provided on a substrate (2). The gas barrier film is further characterized in that: the gas barrier layer (3) has, in at least the thickness direction, a mixed region which includes a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1); and the glass transition temperature of a constituent material of the substrate (2) is at least 150 DEG C.

Description

Gas barrier film and electronic device therewith

The present invention relates to a gas barrier film and an electronic device having the same, and more particularly to a gas barrier film having high gas barrier properties and excellent productivity, and an electronic device having the same.

An inorganic gas barrier layer formed by forming a ruthenium oxide or the like on the surface of a plastic substrate is known as a means for improving the characteristics of various plastic substrates, in particular, gas barrier properties (for example, refer to Patent Document 1).

However, various electronic devices that have been developed and put into practical use in recent years, such as organic electroluminescence (organic EL) devices, solar cells, touch panels, electronic papers, and the like, are not required to have charge leakage, so that a circuit board or the like is formed. A plastic substrate such as a plastic substrate or a film for sealing a circuit board requires high moisture barrier properties. The inorganic gas barrier layer exhibits a higher gas barrier property than an organic film formed by a so-called gas barrier resin or the like, but the properties of the film may be pinholes or cracks in any case. The structural defect or the bonding defect (M-OH bonding) of the gas channel in the MOM network (M is a metal element) constituting the film, as a result, cannot be satisfied by the field of the organic EL element or the like alone. High gas barrier properties require higher gas barrier properties.

As mentioned above, the current state of the art is that it has not been able to achieve the high gas barrier properties of the film in recent years.

On the other hand, a gas barrier film having a gas barrier property on a substrate causes a shrinkage of the substrate due to heat under high temperature and high humidity storage, and cracking occurs in the gas barrier layer, which also causes The problem of reduced gas barrier properties.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-255579

The present invention has been made in view of the above problems and problems, and a problem is to provide a gas barrier film having high gas barrier properties and excellent productivity, and an electronic device including the same.

In order to solve the above problems, the inventors of the present invention have found that the gas barrier layer has a mixed region containing a specific material in at least a thickness direction, and the glass of the constituent material of the substrate is transferred. When the temperature is set to a specific temperature or higher, a gas barrier film and an electronic device having high gas barrier properties and excellent productivity can be provided, and thus the present invention has been completed.

That is, the above problems of the present invention can be solved by the following means.

A gas barrier film characterized by having a gas barrier layer on a substrate, the gas barrier layer having at least a thickness of a transition metal (M2) and a group of 12 to 14 In the mixed region of the transition metal (M1), the glass transition temperature of the constituent material of the substrate is 150 ° C or higher.

2. The gas barrier film according to Item 1, wherein the constituent material of the substrate has a glass transition temperature of 180 ° C or higher.

3. The gas barrier film according to item 2, wherein the constituent material of the substrate is polyimine.

4. The gas barrier film according to Item 1, wherein the gas barrier layer has a region containing the transition metal (M2) or a compound thereof as a main component a (hereinafter referred to as "A region") and contains the aforementioned non-transition a region in which the metal (M1) or a compound thereof is a main component b (hereinafter referred to as "B region"), the mixed region is interposed between the A region and the B region, and the mixed region contains the main component a And a compound of the above main component b.

5. The gas barrier film according to Item 1, wherein when the composition of the mixing region is represented by the following chemical composition formula (1), at least a part of the mixing region satisfies the following relationship (2), and the chemical composition formula (1) ): (M1)(M2) _x O _y N _z Relationship (2): (2y + 3z) / (a + bx) < 1.0 (except, where M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, a: the maximum valence of M1, b: the maximum valence of M2).

6. The gas barrier film of item 1, wherein the non-transition metal (M1) is ruthenium.

An electronic device comprising the gas barrier film according to any one of items 1 to 6.

8. The electronic device according to item 7, which has a resin layer having a content of a sub-point.

9. The electronic device according to item 7, which is provided with an organic electroluminescence element.

According to the above-described means of the present invention, it is possible to provide a gas barrier film having high gas barrier properties and excellent productivity, and an electronic device having the same.

The gas barrier film of the present invention is useful as a substrate or a sealing layer of various electronic devices, and is particularly expected to be practical for organic EL devices, since the gas barrier properties such as moisture barrier properties are remarkably improved and productivity is also excellent. .

A display mechanism for the effects of the present invention. Although the mechanism of action is not clear, it is presumed to be as follows.

According to the review by the inventors of the present invention, a gas barrier layer is formed by using an oxygen-deficient constituent film containing a non-transition metal (M1)-containing compound (for example, an oxide) alone, and a compound containing a transition metal (M2) (for example, an oxide) is used alone. When the oxygen is insufficient to form a gas barrier layer, it is observed that the gas barrier property tends to increase as the degree of oxygen deficiency increases, but it is not related to a significant increase in gas barrier properties.

Based on the result, a region B containing a compound having a non-transition metal (M1) as a main component (for example, an oxide) and a region A containing a compound containing a transition metal (M2) as a main component (for example, an oxide) are laminated. And the mixed region containing the non-transition metal (M1) and the transition metal (M2) is interposed between the A region and the B region, and when the mixed region is made into an oxygen deficiency composition, it is found that the oxygen deficiency is increased. The gas barrier property is significantly improved.

It is considered that, as described above, since the bonding of the non-transition metal (M1) and the transition metal (M2) is more likely to occur than the bonding of the non-transition metal (M1) or the bonding of the transition metal (M2), The mixed region is made of an oxygen-deficient composition, and a high-density structure of a metal compound is formed in the mixed region.

1‧‧‧ gas barrier film

2‧‧‧Substrate

3‧‧‧ gas barrier

10‧‧‧Organic EL components

11‧‧‧Support

12, 14‧‧‧ electrodes

13‧‧‧Organic functional layer

15‧‧‧ Sealing material

100‧‧‧Vacuum ultraviolet light irradiation device

101‧‧‧Device chamber

102‧‧‧Xe excimer lamp

103‧‧‧fixer

104‧‧‧Testing table

105‧‧‧ samples

106‧‧ ‧ visor

Fig. 1 is a cross-sectional view showing a schematic configuration of an example of a gas barrier film of the present invention.

Figure 2 shows the atomic ratio of the gas barrier layer relative to the thickness direction A chart of depth.

3 is a cross-sectional view showing a schematic configuration of an example of an organic EL device including the gas barrier film of the present invention.

Fig. 4 is a schematic view showing an example of a vacuum ultraviolet irradiation device.

The technical feature of the gas barrier film of the present invention is that the gas barrier layer has a mixed region containing a transition metal of Group 5 (M2) and a non-transition metal (M1) of Group 12-14, at least in the thickness direction, and the substrate is The glass transition temperature of the constituent material is 150 ° C or higher. This feature is a common technical feature of the invention of each claim.

As an embodiment of the present invention, the glass transition temperature of the constituent material of the substrate is preferably 180 ° C or more from the viewpoint of high-temperature storage stability, and the constituent material of the substrate is more preferably polyimine.

Further, from the viewpoint of gas barrier properties, the gas barrier layer preferably has an A region containing a transition metal (M2) or a compound thereof as a main component a and a B containing a non-transition metal (M1) or a compound thereof as a main component b. In the region, the mixed region is between the A region and the B region, and the mixed region contains the compound of the source autonomous component a and the main component b.

Further, when the composition of the mixed region is represented by the chemical composition formula (1) from the viewpoint of blocking the intrusion of molecules of gas (water, oxygen, etc.), at least a part of the preferable mixed region satisfies the relationship (2).

Further, based on the same viewpoint, it is preferred that the non-transition metal (M1) is ruthenium.

The gas barrier film of the present invention can be preferably provided in an electronic device. Moreover, the electronic device preferably has a resin layer having a content of a sub-dots. Further, the electronic device preferably includes an organic electroluminescence element.

Hereinafter, the constituent elements of the present invention and the form for carrying out the present invention are described. Detailed description of the situation. In addition, in the present specification, the "~" indicating the numerical range is used in the sense that the numerical values described before and after are included in the lower limit and the upper limit.

Gas barrier film

Fig. 1 is a schematic cross-sectional view showing a gas barrier film 1 of the present invention as an example.

The gas barrier film 1 has a gas barrier layer 3 on the substrate 2.

The gas barrier layer 3 has a mixed region containing a transition metal of Group 5 (M2) and a non-transition metal (M1) of Group 12-14 at least in the thickness direction.

Further, in the present invention, the term "region" means two faces formed when the gas barrier layer is divided at a constant or arbitrary thickness ratio with respect to a surface perpendicular to the thickness direction (lamination direction) of the gas barrier layer. The three-dimensional space (region) between them, the composition of the constituents in the region may be constant in the thickness direction, and may be gradually changed.

In FIG. 1, an example in which the gas barrier layer 3 is provided on only one side of the substrate 2 is shown, but the gas barrier layer 3 may be respectively provided on both sides of the substrate 2, or a plurality of layers may be provided on one surface of the substrate 2. The resulting gas barrier layer 3.

The gas barrier layer 3 preferably has a transition metal (M2) a region in which the compound is a main component a (hereinafter referred to as "A region") and a region containing a non-transition metal (M1) of Group 12 to 14 or a compound thereof as a main component b (hereinafter referred to as "B region"). And a mixed region is interposed between the A region and the B region. At this time, the mixed region contains a compound of the source autonomous component a and the main component b.

The gas barrier layer 3 may not have the A region and the B region, but only the mixed region.

Here, the "a compound of the source autonomous component a and the main component b" means a composite compound in which the main component a and the main component b themselves and the main component a react with the main component b.

When a composite oxide is exemplified as a specific example of the composite compound, the term "composite oxide" means a compound (oxide) formed by chemically bonding constituent components of the A region and the B region. For example, a compound having a chemical structure in which a deuterium atom and a deuterium atom form a chemical bond directly or through an oxygen atom.

Further, in the present invention, a composite in which physical bonding is formed by intermolecular interaction or the like of constituents of the A region and the B region is also included in the "composite compound".

Further, the "principal component" means a component having the largest content in terms of atomic composition ratio. For example, the term "main component of metal" means a metal component having the largest content in terms of the atomic ratio among the metal components in the constituent components.

Further, the term "constituting component" means a compound or a metal or a non-metal monomer constituting a specific region of the gas barrier layer.

Hereinafter, the gas barrier film constituting the present invention is used. Each component is described in detail.

<Substrate>

The base material of the present invention has a glass transition temperature Tg of 150 ° C or more.

Further, as the substrate, a resin substrate is preferable because it can obtain flexibility and light transmittance, and it is more preferably a resin film.

The constituent material of the substrate which can be applied to the present invention is, for example, polyethylene naphthalate (PEN: 155 ° C), alicyclic polyolefin (for example, ZEONOR (registered trademark) 1600 manufactured by ZEON Co., Ltd., Japan: 160 ° C), polyacrylate (PAr: 210 ° C), polyether oxime (PES: 220 ° C), polyfluorene (PSF: 190 ° C), cyclic olefin copolymer (COC: JP-A-2001-150584) Compound: 162 ° C), polyimine (for example, NEOPULIM (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd.: 260 ° C), anthracycline-modified polycarbonate (BCF-PC: for example, JP-A-2000-227603) The compound described in the publication: 225 ° C), an alicyclic modified polycarbonate (IP-PC: for example, a compound described in JP-A-2000-227603: 205 ° C), an acryl-based compound (for example, JP-A-KOKAI) Compound described in JP-A-2002-80616: 300 ° C or higher). Further, the temperature in the brackets indicates the glass transition temperature Tg.

Among them, the constituent material is preferably a glass transition temperature of 180 ° C or higher, more preferably polyimine.

The glass transition temperature Tg of the substrate can be obtained by using an additive or the like And adjust it appropriately.

The thickness of the substrate is preferably in the range of 5 to 500 μm, more preferably in the range of 15 to 250 μm.

For the other types of the substrate which can be used in the present invention, the method for producing the substrate, and the like, for example, the technique disclosed in paragraphs 0125 to 0136 of JP-A-2013-226758 can be suitably employed.

<Gas barrier layer>

As described above, the gas barrier layer of the present invention has a mixed region containing a transition metal of Group 5 (M2) and a non-transition metal (M1) of Group 12-14, at least in the thickness direction. The mixed region may also be interposed between the A region containing the transition metal (M2) or a compound thereof as the main component a and the B region containing the non-transition metal (M1) or a compound thereof as the main component b.

And the preferred aspect of the gas barrier layer is in the mixed region, the ratio of the ratio of the atomic ratio of the transition metal (M2) to the non-transition metal (M1) (the number of atoms of the transition metal (M2) / non-transition metal The region of (M1) atomic number in the range of 0.02 to 49 continuously has 5 nm or more in the thickness direction.

In the A region, the B region, the mixed region, and the gas barrier layer, the term "thickness" or "layer thickness" means the depth in the thickness direction of the gas barrier layer to be described later, which is in the XPS analysis. The sputtering depth is expressed 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 substrate, and the "interface with the substrate" is a gas barrier layer in the composition analysis by XPS (in the present invention The position of the intersection of the elemental distribution of the principal component of the B region and the elemental distribution curve of the principal component of the substrate.

In the mixed region, oxygen is preferably contained in addition to the transition metal (M2) and the non-transition metal (M1). And a preferred form of the mixed region is a mixture of a transition metal (M2) oxide and a non-transition metal (M1) oxide, or a transition metal (M2) and a non-transition metal (M1) composite oxide. In one case, a better form is a composite oxide containing a transition metal (M2) and a non-transition metal (M1).

Here, the "mixture" means a state in which the constituent components of the A region and the B region are not chemically bonded to each other but are mixed. For example, it refers to a state in which cerium oxide and cerium oxide are not chemically bonded to each other but mixed.

The gas barrier property of the gas barrier layer is preferably calculated by forming a gas barrier layer on a substrate to form a laminate, and the oxygen permeability measured according to the method of JIS K 7126-1987 is 1 × 10 ^-3 cm ^{3 .} /(m ² .24h.atm) Hereinafter, the water vapor permeability (25 ± 0.5 ° C, 90 ± 2% RH) measured according to the method of JIS K 7129-1992 is 1 × 10 ^-3 g / (m ² .24h) The following high gas barrier properties.

(A area)

The region A of the present invention contains a transition metal (M2) of a Group 5 element of the long-period periodic table or a compound thereof as a region of the main component a. Here, the "compound" (that is, the compound of the transition metal (M2)" means a compound containing a transition metal (M2), and is, for example, a transition metal oxide.

The transition metal (M2) which is a Group 5 element of the long-period periodic table is exemplified by Nb, Ta, V, and the like.

When the transition metal (M2) is a Group 5 element (particularly Nb), when the non-transition metal (M1) to be described later is Si, the effect of remarkably improving gas barrier properties is obtained. This is considered to be because the bonding of Si to the Group 5 element (especially Nb) is particularly easy to produce. Further, from the viewpoint of optical characteristics, the transition metal (M2) is particularly preferably Nb or Ta which can obtain a compound having good transparency.

The thickness of the A region is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, and more preferably in the range of 5 to 15 nm, from the viewpoint of having both gas barrier properties and optical properties.

(B area)

The B region of the present invention contains a non-transition metal (M1) of a group 12-14 of the long-period periodic table or a compound thereof as a region of the main component b. Here, the "compound", that is, the "non-transition metal (M1) compound" means a compound containing a non-transition metal (M1), and is, for example, a non-transition metal oxide.

The non-transition metal (M1) is not particularly limited, but any of the metals of Groups 12 to 14 may be used alone or in combination, and examples thereof include Si, Al, Zn, In, Sn, and the like. Among them, the non-transition metal (M1) preferably contains Si, Sn or Zn, more preferably Si, and particularly preferably Si alone.

The thickness of the B region is preferably in the range of 10 to 1000 nm, and more preferably based on the viewpoint of both gas barrier properties and productivity. In the range of 20 to 500 nm, it is preferably in the range of 50 to 300 nm.

(mixed area) Mixed area of the invention

(1) A plurality of regions in which chemical constituents of at least a thickness direction of a gas barrier layer are different from each other, and one of the regions (A region) contains a transition metal (M2) or a compound thereof (for example, transition metal oxide) a substance (manganese oxide) or the like, which contains a non-transition metal (M1) or a compound thereof in a region directly or indirectly opposite to the one region (region B), and means a transition metal (M2) derived from the region A And the region of the compound of the non-transition metal (M1) in the B region or (2) the entire region in the gas barrier layer containing the compound derived from the transition metal (M2) and the non-transition metal (M1) means the whole domain.

The preferred aspect of the mixed region is present continuously in a thickness direction of the gas barrier layer by a specific value or more (specifically, 5 nm or more).

When the mixed region has a thickness of at least about 5 nm, high gas barrier properties can be exhibited. Therefore, even when a very thin gas barrier film is formed, high gas barrier properties can be obtained. In other words, the gas barrier film of the present invention has a gas barrier layer which is extremely thin in a gas barrier property, and thus can be a gas barrier film having excellent bending resistance.

The region other than the mixed region of the gas barrier layer may also be an oxide, a nitride, an oxynitride or an oxygen carbon of the non-transition metal (M1). The region of the compound or the like may also be a region of an oxide, a nitride, an oxynitride, an oxycarbide or the like of the transition metal (M2).

(oxygen deficiency composition)

In the present invention, the mixed region contains a non-stoichiometric composition (oxygen deficiency composition) in which a part of the composition is preferably oxygen deficiency.

In the present invention, the oxygen deficiency composition is defined as a composition of the mixed region expressed by the following chemical composition formula (1), and at least a part of the composition of the mixed region satisfies the conditions defined by the following relational expression (2). Further, as the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value of the value obtained by calculating (2y + 3z) / (a + bx) in the mixed region described later is used.

Chemical composition formula (1): (M1) (M2) _x O _y N _z

Relationship (2): (2y + 3z) / (a + bx) < 1.0

(In the formula, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, a: the maximum valence of M1, b: the maximum valence of M2 ).

Hereinafter, when it is not necessary to distinguish particularly, the composition represented by the above 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 transition metal (M2) and the non-transition metal (M1) of the present invention is represented by the chemical composition formula (1). As understood from the composition, the composition of the above composite region may contain a portion of a nitride structure, and it is preferably a nitride-containing material from the viewpoint of gas barrier properties. The composition of the structure.

Here, the maximum valence of the non-transition metal (MM1) 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. Therefore, when the composition of the composite region (including a part of the nitride) is a stoichiometric composition, it is (2y + 3z) / (a + bx) = 1.0. This formula means that the total of the bonding bonds of the non-transition metal (M1) and the transition metal (M2) is the same as the bonding bond of O and N, in which case the non-transition metal (M1) and the transition metal (M2) ) are all bonded to any of O and N. Further, in the present invention, when two or more kinds are used as the non-transition metal (M1), or two or more kinds are used as the transition metal (M2), the maximum valence of each element is weighted by the existence ratio of each element. The average calculated composite price is the value of a and b of the individual "maximum price".

On the other hand, in the mixed region of the present invention, when (2y+3z)/(a+bx)<1.0 is expressed by the relationship (2), it means that the non-transition metal (M1) and the transition metal (M2) The total of the keying bonds is less than the total of the bonding bonds of O and N, and the state is the above-mentioned "oxygen deficiency".

In the oxygen deficiency state, the bonding bonds of the non-transition metal (M1) and the transition metal (M2) are mutually bonded, and if the metals of the non-transition metal (M1) or the transition metal (M2) are directly bonded to each other, A denser structure having a denser density than O or N bonding between metals is formed, and as a result, it is considered that gas barrier properties can be improved.

Further, in the present invention, the mixed region satisfies a region where x has a value of 0.02 ≦ x ≦ 49 (0 < y, 0 ≦ z). This department is defined as the first The ratio of the ratio of the atomic number of the metal (M2) to the non-transition metal (M1) (the number of atoms of the transition metal (M2) / the number of atoms of the non-transition metal (M1)) is in the range of 0.02 to 49, and the thickness is The same definition of the region above 5 nm.

In this region, since both the non-transition metal (M1) and the transition metal (M2) participate in the direct bonding of the metals, it is considered that there is a thickness of a specific value or more (5 nm) by the mixed region satisfying the condition. Helps improve gas barrier properties. Further, the closer the ratio of the non-transition metal (M1) to the transition metal (M2) is, the more it is considered to contribute to the improvement of the gas barrier property. Therefore, the mixed region preferably contains a thickness of 5 nm or more and satisfies 0.1 ≦ x ≦ 10. The region preferably contains a region satisfying 0.2 ≦ x ≦ 5 in a thickness of 5 nm or more, and more preferably a region satisfying 0.3 ≦ x ≦ 4 in a thickness of 5 nm or more.

As described above, in the range of the mixed region, if the relationship of (2y+3z)/(a+bx)<1.0 expressed by the relationship (2) is satisfied, it is confirmed that the gas barrier property can be improved, but the mixture is mixed. The region preferably has at least a part of its composition satisfying (2y+3z)/(a+bx)≦0.9, better satisfying (2y+3z)/(a+bx)≦0.85, and better satisfying (2y+3z)/ (a+bx)≦0.8. Here, the smaller the value of (2y+3z)/(a+bx) in the mixed region, the better the effect of improving the gas barrier property and the greater the absorption of visible light. Therefore, when the gas barrier layer used in the application for transparency is desired, it is preferably 0.2 ≦ (2 y + 3 z) / (a + bx), more preferably 0.3 ≦ (2 y + 3 z) / (a + bx) It is better to be 0.4≦(2y+3z)/(a+bx).

Further, the thickness of the mixed region in which good gas barrier properties are obtained in the present invention is 5 nm or more in terms of the sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and the thickness is preferably 8 nm or more, more preferably 10 nm. Above, it is more preferably 20 nm or more. The thickness of the mixed region is not particularly limited in view of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less from the viewpoint of optical characteristics.

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

(Composition analysis using XPS and thickness measurement of mixed regions)

The composition of the gas barrier layer of the present invention or the composition distribution of the A region and the B region or the thickness of each region can be determined by X-ray photoelectron spectroscope (XPS) as described in detail below. And find it.

Hereinafter, the measurement method using the mixed region of the XPS analysis method, the A region, and the B region will be described.

The element concentration distribution curve (hereinafter referred to as "depth distribution") in the thickness direction of the gas barrier layer of the present invention specifically measures the element concentration of the non-transition metal (M1) (for example, ruthenium) and the transition metal by X-ray photoelectron spectroscopy. (M2) (for example, yttrium) element concentration, oxygen (O), nitrogen (N), carbon (C) element concentration, etc., can be sputtered by a rare gas ion such as argon, and from the surface of the gas barrier layer The inside is exposed and the surface composition analysis is performed in sequence.

The distribution curve obtained by such XPS depth distribution measurement can be prepared, for example, by using the vertical axis as the atomic ratio of each element (unit: at%) and the horizontal axis as the etching time (sputtering time). Further, in the distribution curve of the element having the horizontal axis as the etching time, since the etching time is substantially related to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, the gas barrier is used as the gas barrier. The distance from the surface of the gas barrier layer in the thickness direction of the layer can be calculated from the relationship between the etching rate and the etching time used in the XPS depth distribution measurement from the surface of the gas barrier layer. Further, as the sputtering method used in the measurement of the XPS depth distribution, it is preferable to use a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species, and the etching rate (etching rate) thereof is set to 0.05 nm/second. (SiO ₂ thermal oxide film conversion value).

An example of specific conditions of the XPS analysis applicable to the composition analysis of the gas barrier layer of the present invention is shown below.

. Analytical device: QUANTERA SXM manufactured by ULVAC PHI

. X-ray source: monochromated Al-Kα

. Sputtering ions: Ar (2keV)

. Depth distribution: The thickness was sputtered in terms of SiO ₂ , and the measurement was repeated at specific thickness intervals to determine the depth distribution in the depth direction. The thickness interval is set to 1 nm (data per 1 nm in the depth direction is obtained)

. Quantification: The background was determined by the Shirley method, and the relative peak area was quantified using the relative sensitivity coefficient method. The data processing system uses MultiPak manufactured by ULVAC PHI. Also, the element of analysis is non-transition metal (M1) (for example, bismuth (Si)), transition metal (M2) (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C).

Calculating the composition ratio from the obtained data, and determining the ratio of the ratio of the atomic ratio of the transition metal (M2) to the non-transition metal (M1) coexisting with the non-transition metal (M1) and the transition metal (M2) (transition metal (M2) The atomic ratio/non-transition metal (M1) atomic ratio) is in the range of 0.02 to 49, and is defined as a mixed region to determine the thickness. The thickness of the mixed region is expressed in terms of SiO ₂ in terms of the sputter depth in the XPS analysis.

Specific examples of the mixed region in the gas barrier layer of the present invention will be described below using a map.

2 is a graph showing the distribution of elements and the mixed region when the composition distribution of the non-transition metal (M1) and the transition metal (M2) in the thickness direction of the gas barrier layer is analyzed by the XPS method.

In FIG. 2, the elemental analysis of the non-transition metal (M1), the transition metal (M2), O, N, and C is performed in a direction deeper than the surface of the gas barrier layer (the surface opposite to the substrate), and is represented on the horizontal axis. The sputtering depth (nm: SiO ₂ conversion), and the vertical axis represents a graph of the content ratio (at %) of the non-transition metal (M1) and the transition metal (M2).

From the side of the substrate, a B region composed of an element having a metal as a main component of a non-transition metal (M1) (for example, Si) is shown, and a surface of the gas barrier layer which is in contact therewith is shown as a metal as a transition metal (M2). (for example, 铌) A region composed of elements of the main component. The ratio of the atomic ratio of the transition metal (M2) to the non-transition metal (M1) in the mixed region The value (the atomic number ratio of the transition metal (M2) / the atomic number ratio of the non-transition metal (M1)) is an area represented by the element composition in the range of 0.02 to 49, and one part of the A area overlaps with one of the B areas. The region is a region having a thickness of 5 nm or more.

<Method of forming each region> (Formation method of area A)

The method for forming the A region containing the transition metal (M2) is not particularly limited. For example, when a conventional vapor phase film formation method using a conventional thin film deposition technique is used, it is preferable to form a mixed region efficiently.

A conventional method can be used for the vapor phase film formation method. The vapor phase film formation method is not particularly limited, and examples thereof include a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, and an ion assist vapor deposition method, and a plasma CVD method. (Chemical Vapor Deposition) method, chemical vapor phase growth (CVD) method such as ALD (Atomic Layer Deposition) method. Among them, it is preferably formed by a physical vapor phase growth (PVD) method, and is preferably formed by a sputtering method, because it can form a film without causing damage to a functional element and has high productivity.

The film formation by the sputtering method may be two or more types using two-pole sputtering, magnetron sputtering, double magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like. Further, any of DC (direct current) sputtering or RF (high frequency) sputtering in which the target is applied depending on the target species may be used.

Further, a reactive sputtering method using a transition mode between the metal mode and the oxide mode can also be used. It is preferable to control the sputtering phenomenon so as to become a transition region, since the metal oxide can be formed at a high film formation rate.

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. Further, a film of a composite oxide, an oxynitride, an oxycarbide or the like of a non-transition metal (M1) and a transition metal (M2) can be formed by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas. The film formation conditions in the sputtering method are, for example, application of electric power, discharge current, discharge voltage, time, and the like, but these may be appropriately selected depending on the sputtering apparatus, the film material, the thickness, and the like.

The sputtering method can also be a multi-layer simultaneous sputtering method using a plurality of key plating target materials containing a transition metal (M2)-containing monomer or an oxide thereof. For the method of producing the sputtering target or the method of producing a film formed using the composite oxide of the sputtering target, for example, JP-A-2000-160331, JP-A-2004-068109 The method or condition described in Japanese Laid-Open Patent Publication No. 2013-047361.

The film formation conditions in the case of performing the co-deposition method include, for example, a ratio of a transition metal (M2) to oxygen from a film-forming raw material, a ratio of an inert gas to a reactive gas at the time of film formation, a gas supply amount at the time of film formation, and One or two or more kinds of conditions selected from the group consisting of the degree of vacuum at the time of film formation and the electric power at the time of film formation can be formed by adjusting the film forming conditions (preferably, oxygen partial pressure). A mixture of composite oxides composed of a composition. That is, using the co-evaporation method as described above to form a gas barrier layer, the gas formed Almost the entire thickness direction of the bulk barrier layer can be a mixed region. According to this method, the desired gas barrier property can be achieved by extremely simple operation of controlling the thickness of the mixed region. Further, when controlling the thickness of the mixing region, for example, the film formation time in the case of performing the co-deposition method may be adjusted.

(Method of forming Area B)

The method for forming the B region containing the non-transition metal (M1) is not particularly limited, and for example, a conventional method can be used for the vapor phase film formation method. The vapor phase film formation method is not particularly limited, and examples thereof include a physical vapor phase growth (PVD) method, a plasma CVD method, and an ALD method such as a sputtering method, a vapor deposition method, an ion plating method, and an ion assist vapor deposition method. Chemical vapor phase growth (CVD) method. Among them, based on the viewpoint that film formation and high productivity are not caused by damage to functional elements, it is preferably formed by a physical vapor phase growth (PVD) method, and a non-transition metal (M1) can be used by sputtering. It is formed as a target.

Further, as another method, a method of forming a coating liquid containing polyazane containing Si as a non-transition metal (M1) is also one of preferable methods.

In the present invention, it is applicable to a polymer having a ruthenium-nitrogen bond in a "polyazane" structure formed in the B region, and is a SiO ₂ or Si ₃ N made of Si-N, Si-H, NH or the like. ₄ and a ceramic precursor inorganic polymer such as an intermediate solid solution SiO _x N _y .

In order to form the B region constituting the gas barrier layer by using polyazane, for example, it is preferable to change the temperature at a relatively low temperature as described in Japanese Laid-Open Patent Publication No. Hei 8-112879. Sex A polyazane of cerium oxide, cerium nitride or cerium oxynitride.

The polyazide is exemplified by a compound having a structure represented by the following formula (1).

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

In the present invention, from the viewpoint of the denseness of the film in the B region, it is preferable that all of R ₁ , R ₂ and R ₃ are hydrogen-containing perhydropolyazane (PHPS).

On the other hand, an organopolyazane having a part of a hydrogen atom bonded to the Si via an alkyl group or the like can have an alkyl group such as a methyl group to improve adhesion to an adjacent substrate, and even if it is hard Further, the brittleness can also make the ceramic film tough by polyazane, and it is preferable in terms of suppressing the occurrence of cracks when the B region is thicker.

These perhydropolyazane and the organopolyazane may be appropriately selected depending on the use, and may be used in combination.

Further, the perhydropolyazane is presumed to have a structure in which a linear structure and a ring structure centering on a 6- or 8-membered ring coexist.

The molecular weight of the polyazane, the number average molecular weight (Mn) is About 600 to 2000 (in terms of polystyrene), the substance which is liquid or solid varies with molecular weight.

These polyazide compounds are commercially available in the form of a solution dissolved in an organic solvent, and commercially available products can be directly used as a coating liquid containing a polyazide compound.

The other example of the polyazane which is ceramized at a low temperature is exemplified by the addition of the polyazide to the alkoxylated oxime and the addition of polyazide (Japanese Patent Laid-Open No. Hei 5-238827). The glycidol obtained by the glycidol reaction is added to polyazide (Japanese Unexamined Patent Publication No. Hei No. Hei. No. 6-122852), and the alcohol-added polyazide obtained by the reaction with an alcohol (JP-A-6-240208) The addition of the metal carboxylate obtained by the acid salt reaction to the polyoxazide (Japanese Patent Laid-Open No. Hei 6-299118), and the addition of the acetamidine pyruvate complex obtained from the metal-containing acetoacetate complex. In the case of the metal fine particles obtained by adding the metal fine particles, polyazane (Japanese Patent Laid-Open Publication No. Hei 7-196986) and the like are added.

In addition, for the details of the polyazide, for example, paragraphs 0024 to 0040 of JP-A-2013-255910, paragraphs 0037 to 0043 of JP-A-2013-188942, and JP-A-2013-151123 Paragraphs 0014 to 0021, paragraphs 0033 to 0045 of JP-A-2013-052569, paragraphs 0062 to 0075 of JP-A-2013-129557, and paragraphs 0037 to 0064 of JP-A-2013-226758, and the like. The content and application.

As an organic solvent for preparing a coating liquid containing polyazane It is preferred to avoid the use of an alcohol system or a water containing substance which is easily reacted with polyazane. As a preferable organic solvent, for example, a hydrocarbon solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon, a halogenated hydrocarbon solvent, or an ether such as an aliphatic ether or an alicyclic ether can be used. Specific examples thereof include a hydrocarbon such as pentane, hexane, cyclohexane, toluene, xylene, an aromatic solvent (Solvesso), and a halogenated hydrocarbon such as dichloromethane or trichloroethane. An ether such as ether, dioxane or tetrahydrofuran.

These organic solvents may be selected based on the purpose of the solubility of the polyazane or the volatilization rate of the solvent, or a plurality of organic solvents may be mixed.

The concentration of polyazane in the coating liquid containing polyazane varies depending on the thickness of the gas barrier layer to be used or the service life of the coating liquid, but is preferably about 0.2 to 35% by mass.

Further, in the coating liquid containing polyazane, a catalyst for promoting an amine or a metal modified with cerium oxide, cerium nitride or cerium oxynitride may be added. For example, a polyfluorene-containing nitrogen containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product can be used. Alkane solution. These commercially available products may be used singly or in combination of two or more.

Further, in the coating liquid containing polyazane, the amount of catalyst added is preferably adjusted for polyxazane in order to avoid excessive formation of stanol by the catalyst, decrease in film density, increase in film defects, and the like. It is 2% by mass or less.

In the coating liquid containing polyazane, in addition to polyazane In addition, inorganic precursor compounds may also be included. The inorganic precursor compound other than polyazane is not particularly limited as long as it can prepare a coating liquid. For example, a compound other than the polyazane described in paragraphs 1010 to 0114 of JP-A-2011-143577 can be suitably used.

(adding elements)

In the coating liquid containing polyazane, an organometallic compound of a metal element other than Si may be added. By adding an organometallic compound of a metal element other than Si, during the coating and drying process, the substitution of the N atom and the O atom of the polyazane can be promoted, and after the coating is dried, it can be changed to a stable composition close to SiO ₂ .

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

Particularly preferred are Al, B, Ti and Zr, of which an organometallic compound containing Al is preferred.

The aluminum compound which can be suitably used in the present invention can be exemplified by, for example, isopropyl aluminum oxide, aluminum second butyrate, titanium isopropoxide, aluminum triacetate, aluminum triisopropylate, aluminum trisuccinate, and aluminum tri-n-butyrate. , three second aluminum butyrate, ethyl acetonitrile acetic acid. Aluminum diisopropylate, acetoxy aluminum diisopropylate, two Aluminum isopropylate monobutoxide, aluminum triethylacetate acetate, alumina isopropoxide trimer, and the like.

As specific commercial products, for example, AMD (diisopropyltin monobutyric acid aluminum butyrate), ASBD (second aluminum butyrate), ALCH (ethylacetamidineacetic acid. aluminum diisopropylate), ALCH-TR (triethyl acetonitrile aluminum acetate), aluminum chelate M (alkyl acetonitrile acetic acid. aluminum diisopropylate), aluminum chelate D (diethyl acetamidine acetic acid. monoethyl acetonate pyruvate), Aluminum chelate A (W) (aluminum triacetate pyruvate) (the above is manufactured by Kawasaki Precision Chemical Co., Ltd.), PLENACT (registered trademark) AL-M (acetoxy aluminoxy diisopropylate, Ajinomoto Precision Chemical Co., Ltd.) and so on.

Further, when these compounds are used, it is preferably mixed with a coating liquid containing polyazane in an inert gas atmosphere. In order to suppress the reaction of these compounds with moisture or oxygen in the atmosphere, inhibition of oxidation is intense.

Further, when these compounds are mixed with polyazane, the temperature is preferably raised to 30 to 100 ° C and maintained for 1 minute to 24 hours while stirring.

The content of the above-mentioned added metal element in the polyazinium-containing layer constituting the gas barrier layer of the present invention is preferably in the range of 0.05 to 10 mol%, more preferably 0.5 to 5 mol%, for the cerium (Si) content of 100 mol%. Within the scope.

(upgrading treatment)

In the formation of the B region using polyazane, it is preferred to carry out a modification treatment after forming the polyazide-containing layer.

The so-called reforming treatment imparts energy to the polyazane, and converts part or all of it into cerium oxide or cerium oxynitride.

The upgrading treatment in the present invention can be selected based on a conversion reaction of polyazane, and examples thereof include a conventional plasma treatment, a plasma ion implantation treatment, an ultraviolet irradiation treatment, a vacuum ultraviolet irradiation treatment, and the like. In the present invention, it is preferred to use a plasma, ozone or ultraviolet light conversion reaction which can carry out a conversion reaction at a low temperature. Conventional methods can be used by the conversion reaction of plasma or ozone. In the present invention, it is preferably applied to a coating film containing a polyazide-containing coating liquid having a coating method on a substrate, and irradiated with a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less and subjected to a vacuum ultraviolet irradiation treatment of a modified treatment. Method of gas barrier layer.

As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used, and examples thereof include an excimer lamp (a single wavelength such as 172 nm, 222 nm, and 308 nm, for example, manufactured by USHIO Electric Co., Ltd., manufactured by MDCOM Co., Ltd., etc.).

The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm greater than the interatomic bonding force in polyazane, preferably using light energy of a wavelength of 100 to 180 nm, by photon only called photon quantum process The method of performing the oxidation reaction of active oxygen or ozone while directly cutting off the bond of the atom, and performing the formation of the ruthenium oxide film at a relatively low temperature (about 200 ° C or lower).

For details of such reforming treatment, for example, paragraphs 0055 to 0091 of JP-A-2012-086394, paragraphs 0049 to 0085 of JP-A-2012-006154, and paragraph 0046 of JP-A-2011-251460 The contents described in ~0074 and the like.

(Method of forming mixed area)

As a method of forming the mixed region, it is preferred to form a mixed region between the A region and the B region by appropriately adjusting the respective forming conditions when forming the A region and the B region as described above.

When the B region is formed by the vapor phase film formation method, the ratio of the non-transition metal (M1) to the oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas at the time of film formation, and the film formation are adjusted. A mixed region can be formed by one or two or more kinds of the gas supply amount, the degree of vacuum at the time of film formation, the magnetic force at the time of film formation, and the electric power at the time of film formation.

When the B region is formed by the above-described coating film formation method, the film formation material (polyazoxide species, etc.), the catalyst species, the catalyst content, and the coating film are, for example, adjusted by a non-transition metal (M1)-containing film formation material. Thick, dry temperature. One or two or more kinds of conditions selected by the time, the modification method, and the modification conditions can form a mixed region.

When the A region is formed by the vapor phase film formation method, the ratio of the transition metal (M2) to the oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas at the time of film formation, and the film formation are adjusted. A mixed region can be formed by one or two or more kinds of the gas supply amount, the degree of vacuum at the time of film formation, the magnetic force at the time of film formation, and the electric power at the time of film formation.

Further, in the above method, controlling the thickness of the mixed region can be controlled by appropriately adjusting the formation conditions of the method for forming the A region and the B region. For example, when the A region is formed by a vapor phase film formation method, the desired film thickness can be obtained by controlling the film formation time. Further, it is also preferably a method of directly forming a mixed region of the non-transition metal (M1) and the transition metal (M2).

As a method of directly forming a mixed region, a conventional co-evaporation method is preferably used. As such a co-evaporation method, a co-sputter method is preferably exemplified. The common sputtering method used in the present invention is a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a non-transition metal (M1) and a transition metal (M2). The composite target made of the composite oxide serves as a single target for the sputtering target.

Moreover, the co-sputtering method in the present invention may also be a multi-component sputtering target using a non-transition metal (M1)-containing monomer or an oxide thereof and a transition metal (M2) monomer or an oxide thereof. Sputtering. For a method of producing the sputtering target or a method of producing a film made of a composite oxide using the sputtering target, for example, JP-A-2000-160331, JP-A-2004-068109 Japanese Unexamined Patent Publication No. 2013-047361, and the like.

Further, the film formation conditions in the case of performing the co-evaporation method are exemplified by the ratio of the transition metal (M2) to oxygen in the film formation raw material, the ratio of the inert gas to the reactive gas at the time of film formation, and the gas supply at the time of film formation. One or two or more kinds of conditions selected by the amount of the film, the degree of vacuum at the time of film formation, and the electric power at the time of film formation can be formed by adjusting the film forming conditions (preferably, oxygen partial pressure). Lack of composition of the film. That is, by forming the gas barrier layer by the co-evaporation method as described above, a substantially uniform region in the thickness direction of the formed gas barrier layer can be formed as a mixed region. Therefore, by such a method, the desired gas barrier property can be achieved by extremely simple operation of controlling the thickness of the mixed region. Further, when controlling the thickness of the mixed region, for example, the film formation time at the time of performing the co-deposition method may be adjusted.

<Other functional layers>

In the gas barrier film of the present invention, in addition to the constituent layers described above, other functional layers may be provided insofar as the effects of the object of the present invention are not impaired.

(anchor coating)

The surface of the substrate on the side of the gas barrier layer of the present invention may be provided with an anchor coating for the purpose of improving the adhesion between the substrate and the gas barrier layer.

The anchor coating agent used for anchoring the coating layer may be used singly or in combination of two or more kinds thereof, such as a polyester resin, an isocyanate resin, a urethane resin, an acrylic resin, an ethylene vinyl alcohol resin, an ethylene modified resin, or an epoxy resin. , modified styrene resin, modified siloxane resin, alkyl titanate and the like.

Conventional additives may be added to the anchor coating agents. Further, the anchor coating agent may be applied to a substrate by a conventional method such as roll coating, gravure coating, blade coating, dip coating, spray coating or the like to dry the solvent, the diluent, and the like. And anchor coating. The coating amount of the anchor coating agent is preferably about 0.1 to 5.0 g/m ² (dry state).

Further, the anchor coating layer may be formed by a vapor phase film formation method by a physical vapor deposition method or a chemical vapor deposition method. For example, an inorganic film mainly composed of ruthenium oxide can be formed for the purpose of improving adhesion and the like as described in JP-A-2008-142941. Also, by, for example, Japan Special Edition 2004- An anchor coating layer is formed as described in Japanese Patent No. 314626, and when an inorganic thin film is formed by a vapor phase film formation method, a gas generated from the substrate side is blocked to some extent, and an anchor is formed for the purpose of controlling the composition of the inorganic thin film. Set the coating.

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

(transparent hard coating)

A transparent hard coat layer may also be disposed on the surface of the substrate (single or double sided). An example of the material contained in the transparent hard coat layer is a thermosetting resin or an active energy ray-curable resin, but it is preferably an active energy ray-curable resin because it is easy to form. These curable resins may be used alone or in combination of two or more.

The active energy ray-curable resin means a resin which is hardened by a crosslinking reaction or the like by irradiation with an active energy ray such as ultraviolet rays or electron beams. As the active energy ray-curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and is cured by irradiation with an active energy ray such as ultraviolet rays or electron beams to form a cured product containing an active energy ray-curable resin. The layer, which is a transparent hard coat. The active energy ray-curable resin is exemplified by an ultraviolet curable resin or an electron beam curable resin, but is preferably an ultraviolet curable resin which is cured by ultraviolet irradiation. A commercially available substrate in which a transparent hard coat layer is formed in advance can also be used.

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

The active energy ray-curable resin which is suitable as a material for forming a transparent hard coat layer is exemplified by, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, an acrylate compound and sulfur having a thiol group. A resin composition of an alcohol compound, an epoxy acrylate, a urethane acrylate, a polyester acrylate, a polyether acrylate, a polyethylene glycol acrylate, a glycerin methacrylate, or the like, in which a polyfunctional acrylate is dissolved A monomer resin composition or the like. Specifically, a UV-curable organic/inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Co., Ltd. can be used. In addition, any mixture of the above-mentioned resin compositions may be used, and a photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule is not particularly limited.

Specific examples of the thermosetting material include TUTTO PROM series (organic polyazide) manufactured by CLARIANT Co., Ltd., SO COAT heat-resistant transparent coating manufactured by CERAMIC COAT Co., Ltd., NANOHYBRID SILICON manufactured by ADEKA Co., Ltd., and DIC Co., Ltd. UNIDIC (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (super high heat resistance epoxy resin), various polyoxyl resins manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Nitto Textile Co., Ltd. Inorganic. Organic nanocomposite SSG COAT, thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, polyoxyn resin Wait. Among these, in particular, a material based on an epoxy resin having heat resistance.

The method for forming the transparent hard coat layer is not particularly limited, but is preferably formed by a dry coating method such as a spin coating method, a spray method, a knife coating method, or a dipping method, or a dry coating method such as a vapor deposition method. .

In the formation of the transparent hard coat layer, an additive such as an antioxidant, an ultraviolet absorber, or a plasticizer may be added to the active energy ray-curable resin as needed. Further, it is not related to the lamination position of the transparent hard coat layer, and any of the transparent hard coat layers may be a suitable resin or additive in order to improve film formability and prevent occurrence of pinholes in the film.

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

Electronic Devices

The gas barrier film of the present invention can be suitably applied to an electronic device which deteriorates performance due to chemical components (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.) in the air.

Examples of the electronic device body used in the electronic device having the gas barrier film of the present invention include, for example, a QD film having a resin layer of a sub-dot (QD) layer, an organic electroluminescence device (organic EL device), and a liquid crystal display device. (LCD), thin film transistor, touch panel, electronic paper, solar cell (PV), and the like. The electronic device body is preferably an organic EL element or a solar cell, more preferably an organic EL element, from the viewpoint of more effectively obtaining the effect of the present invention.

<Quantum dot (QD) film>

The gas barrier film of the present invention can be applied to a QD film having a content of a sub-dots.

Hereinafter, a quantum dot (QD) including a main component of the QD resin layer, a resin, and the like will be described.

(quantum dot)

Generally, a semiconductor nanoparticle which is a semiconductor material of a nanometer size and exhibits a quantum confinement effect is also referred to as a "quantum dot". The quantum dots are small pieces of semiconductor atoms that are gathered in the range of several hundred to several thousand or so, and absorb light from the excitation source to reach an energy excitation state, thereby releasing energy equivalent to the energy band gap of the quantum dots. .

Therefore, quantum dots are known to have unique optical properties by quantum size effects. Specifically, it has the following features: (1) by controlling the particle size, light of various wavelengths and colors can be emitted, (2) absorption band is wide, and light of various sizes can be emitted by excitation light of a single wavelength, (3) The fluorescence spectrum is a good symmetrical shape, and (4) it is excellent in durability and fading resistance as compared with the organic dye.

The quantum dots contained in the QD-containing resin layer may be conventionally used, and may be produced by any conventional method. For example, a preferred quantum dot and a method for forming the same are exemplified by US Pat. No. 6,225, 198, U.S. Patent Application Publication No. 2002/0066401, U.S. Patent No. 6,207,229, U.S. Patent No. 6,302,901, U.S. Patent No. It is described in the specification of No. 6,949,206, the specification of U.S. Patent No. 7,572, 393, the specification of U.S. Patent No. 7,267,865, the specification of U.S. Patent No. 7,374,807, the U.S. Patent Application No. 11/299,299, and the specification of U.S. Patent No. 6,861,155.

The quantum dots are formed of any suitable material, preferably an inorganic material, more preferably an inorganic conductor or a semiconductor material. Suitable semiconductor materials include semiconductors of Groups II-VI, III-V, IV-VI, and IV, including any type of semiconductor.

Suitable semiconductor materials may 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 CO, and a suitable combination of two or more of these semiconductors are not limited thereto.

In the present invention, core/shell type quantum dots such as CdSe/ZnS, InP/ZnS, PnSe/PbS, CdSe/CdS, CdTe/CdS, CdTe/ZnS, and the like can be preferably used.

(content sub-dot (QD) resin layer)

In the QD-containing resin layer, a resin which is a binder for holding quantum dots can be used. For example, a polyester system such as a polycarbonate system, a polyacrylate type, a polyfluorene (including a polyether oxime) system, a polyethylene terephthalate or a polyethylene naphthalate, a polyethylene system, or a poly Cellulose esters such as propylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinylidene chloride , polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethyl decene, polyether ketone, polyether ketoximine, polyamine An acrylic resin such as a resin, a fluororesin, a nylon or a polymethyl methacrylate.

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

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

Organic EL Components

A representative example of an electronic device to which the gas barrier film of the present invention is applied is exemplified by an organic EL element as shown in FIG. As shown in FIG. 3, the organic EL element 10 includes a pair of electrodes 12 and 14 on the support 11, an organic functional layer 13 between the pair of electrodes 12 and 14, and a sealing material 15 covering the organic functional layer 13. As the support 11, the gas barrier film 1 of the present invention can be applied.

The organic functional layer 13 is provided with at least a light-emitting layer, as needed A hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like are prepared.

The light-emitting layer contains a light-emitting organic compound or an organic metal complex or the like, and is directly injected or injected from another electrode (cathode) by directly injecting a hole injected from an electrode (anode) or from an anode through a hole transport layer or the like. The injected electrons such as the electron transport layer recombine to emit light.

The organic functional layer 13 or the electrodes 12 and 14 are easily deteriorated by intrusion of gas such as oxygen or water in the atmosphere. The organic EL element 10 includes the gas barrier film 1 as the support 11 in order to suppress the deterioration of the light-emitting performance due to the deterioration of the organic functional layer 13 or the like. However, the gas barrier film 1 may be provided as the sealing material 15 .

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto.

[Example 1] "Production of Gas Barrier Films"

Gas barrier films 101 to 109 were produced in accordance with the following methods.

<Production of Gas Barrier Film 101> (1) Preparation of the substrate

A polyethylene terephthalate film having a thickness of 100 μm which is easily treated on both sides (manufactured by TORAY Co., Ltd., LUMIRROR) The transparent hard coat layer 1 (back side) and the transparent hard coat layer 2 (gas barrier layer forming surface side) were formed on both surfaces of the trademark U48 (referred to as PET film).

(formation of transparent hard coating)

The UV-curable resin was applied by wet coating on the back side of the PET film (the side opposite to the side on which the gas barrier layer was formed) so that the dry layer thickness was 0.5 μm (AICA Industrial Co., Ltd.) After the company's system, product number: Z731L), the formed coating film was dried at 80 ° C, and then hardened under high air mercury lamp with an irradiation energy of 0.5 J/cm ^{2 to} form a transparent hard coat layer 1 on the back side. .

Next, on the surface of the PET film (the surface on which the gas barrier layer is formed), a UV-curable resin "OPSTAR (registered trademark) Z7527" manufactured by JSR Co., Ltd. was used to wet the layer to a thickness of 2 μm. After coating by the coating method, it was dried at 80 ° C, and then hardened under air using a high-pressure mercury lamp at an irradiation energy of 0.5 J/cm ^{2 to} form a transparent hard coat layer 2 having a thickness of 2 μm on the surface side.

(2) Formation of gas barrier layer (Formation of a film containing a non-transition metal (M1))

On the side of the substrate to form the transparent hard coat layer 2, by gas phase method. Sputtering (magnetron sputtering device manufactured by CANON ANELVA, Form EB1100) forms a film containing a non-transition metal (M1). The sputtering device used is a binary simultaneous sputtering.

Here, a polycrystalline germanium target was used as a target, and a mixed gas of Ar and O ₂ was used as a process gas, and a film was formed to have a thickness of 55 nm by DC sputtering. The sputtering power supply was set to 5.0 W/cm ² and the film formation pressure was set to 0.4 Pa. The film formation is carried out by adjusting the oxygen partial pressure so that the composition becomes SiO ₂ . Further, the film formation was carried out in advance using a glass substrate, and the composition conditions were set by adjusting the oxygen partial pressure, and the conditions were obtained in which the composition near the surface layer depth of 10 nm was changed to SiO ₂ . Further, regarding the thickness, the thickness of the film formation time is measured in the range of 100 to 300 nm, and the thickness of the film formed per unit time is calculated, and then the film formation time is set so as to be the set thickness.

By the above method, a film having a composition of non-transition metal oxide SiO _{2 was} formed on one surface side of the substrate at a thickness of 55 nm.

(Formation of a film containing a transition metal (M2))

On the above-mentioned film containing non-transition metal (M1), by gas phase method. Sputtering (magnetron sputtering device manufactured by CANON ANELVA, Form EB1100) forms a film containing a transition metal (M2).

A commercially available metal Nb target was used as a target, and a mixed gas of Ar and O ₂ was used as a process gas, and a film was formed to have a thickness of 10 nm by DC sputtering. The sputtering power supply was set to 5.0 W/cm ² and the film formation pressure was set to 0.4 Pa. In the film formation conditions, the oxygen partial pressure was set to 12%. In addition, film formation was performed in advance using a glass substrate, and in the film formation conditions, data on the thickness change of the film formation time was taken, and the thickness of the film formed per unit time was calculated, and then the film formation time was set so as to be the set thickness.

From the above, a gas barrier layer having a layer thickness of 65 nm was formed.

(3) XPS analysis of gas barrier layer

The composition distribution profile from the surface side of the gas barrier layer in the thickness direction was determined by XPS analysis. Also, the XPS analysis conditions are as follows. In addition, the sample used in the analysis was prepared at 20 ° C after using the sample. Samples stored in a 50% RH environment.

(XPS analysis conditions)

. Device: QUANTERA SXM manufactured by ULVAC PHI

. X-ray source: monochromated Al-Kα

. Sputtering ions: Ar (2keV)

. Depth distribution: The thickness was sputtered in terms of SiO ₂ , and the measurement was repeated at specific thickness intervals to determine the depth distribution in the depth direction. The thickness interval is set to 1 nm (data per 1 nm in the depth direction is obtained)

. Quantification: The background was determined by the Shirley method, and the relative peak area was quantified using the relative sensitivity coefficient method. The data processing system uses MultiPak manufactured by ULVAC PHI. Further, the elements of the analysis are non-transition metal (Si), transition metal (Nb), O, N, and C.

(4) Calculation of oxygen deficiency index (2y+3z)/(a+bx) in the mixed region

Calculate the value of the oxygen deficiency index (2y+3z)/(a+bx) in the mixed region. Here, a is the maximum valence of Si (M1) of 4, and b is the maximum valence of 5 of Nb (M2). And x, y and z are determined by XPS analysis. The ratio of the ratio of the number of individual atoms of Nb (M2), O, and N when the atomic ratio of Si (M1) is 1. Next, the minimum value of (2y+3z)/(a+bx) in the mixed region is determined as an oxygen deficiency index, and when the minimum value is less than 1.0, it is determined that the mixed region is in an oxygen deficiency state.

<Production of Gas Barrier Films 102 to 104>

In the production of the gas barrier film 101, the gas barrier films 102 to 104 were produced in the same manner except that the substrate was changed to the one shown in Table 1.

PEN: Teijin Co., Ltd., TEONEX

PES: Sumitomo Chemical Co., Ltd. SUMIKA EXCEL4010GL30

PI: NEOPLEM manufactured by Mitsubishi Gas Chemical Co., Ltd.

<Production of Gas Barrier Film 105>

In the production of the gas barrier film 104, the gas barrier property was similarly produced except that the target material when the film containing the non-transition metal (M1) was formed was changed to alumina (refractive index: 1.63) and the film was formed to have a thickness of 70 nm. Film 105.

<Production of Gas Barrier Films 106 to 108>

In the production of the gas barrier films 102 to 104, the gas barrier films 106 to 108 were produced separately except that the target material was changed to a metal Ta target and the film was formed to have a thickness of 10 nm. .

<Production of Gas Barrier Film 109>

In the production of the gas barrier film 104, a gas barrier film 109 was produced in the same manner as the gas barrier layer as described below.

(formation of gas barrier layer)

On the side of the substrate on which the transparent hard coat layer 2 is formed, a polycrystalline germanium target and a metal Nb target are used as targets, and Ar and O _{2 are} used as process gases, and a dual sputtering method of co-sputtering by DC method is used. Plating, forming a gas barrier layer. The power supply of the polycrystalline germanium target and the power supply of the metal Nb target were adjusted in such a manner that the partial pressure of oxygen was set to 18% and the atomic ratio of Si to Nb in the film became the same amount. The film formation time was set so that the layer thickness was 50 nm.

"Evaluation"

The water vapor permeability and storage stability of each of the gas barrier films produced were evaluated as follows.

The evaluation results are shown in Table 1.

<Measurement of water vapor transmission>

The water permeability (water vapor permeability) of each of the produced gas barrier films was measured according to the following measurement method, and the water vapor barrier property was evaluated.

Further, the gas barrier film of the present invention is not limited to a method for measuring the degree of water vapor permeability. In the present embodiment, the Ca method is used as a method for measuring the degree of water vapor permeability.

(using the device)

Evaporation unit: Japan E-stock (vacuum) vacuum evaporation unit JEE-400

Constant temperature and humidity oven: Yamato Humidic Chamber IG47M

(evaluation material)

Corrosive metal reacted with moisture: calcium (granular)

Water vapor impermeable metal: aluminum ( 3~5mm, granular)

(Production of cell for water vapor barrier evaluation)

Metallic calcium was vapor-deposited except for the vapor deposition portion (12 mm × 12 mm 9 portion) of the gas barrier layer of the sample, which was subjected to a vacuum deposition apparatus (JE-400, Japan Electron Vacuum Evaporation Apparatus). Subsequently, the mask is directly removed in a vacuum state, and aluminum is vapor-deposited from another metal evaporation source on one side of the sheet. After the aluminum was sealed, the vacuum was released, and the resin was quickly moved to a dry nitrogen atmosphere, and a quartz glass having a thickness of 0.2 mm was attached to the aluminum vapor deposition surface through a sealing ultraviolet curing resin (manufactured by NAGESE CHEMTEX Co., Ltd.), and ultraviolet rays were irradiated to harden the resin. The company is officially sealed to produce a unit for evaluating water vapor barrier properties.

Then use a constant temperature and humidity oven, the evaluation unit obtained at 60 ° C. The 90% RH was stored under high temperature and high humidity, and the amount of moisture in the permeation unit (g/(m ² .24h)) was calculated from the amount of corrosion of the metal calcium based on the method described in JP-A-2005-283561.

In addition, in order to confirm that the water vapor other than the gas barrier film surface is not transparent After replacing the gas barrier film sample, the unit for vapor deposition of metal calcium on a quartz glass plate having a thickness of 0.2 mm is used as a comparative sample, and is also at 60 ° C. The 90% RH was stored under high temperature and high humidity, and it was confirmed that no corrosion of metal calcium occurred after 1000 hours.

<Evaluation of preservation (crack evaluation)>

For the gas barrier film produced, a sample of size 300mm × 300mm is at 85 ° C. After storing for 14 days in an environment of 85% RH, the amount of permeated water (water vapor transmission rate) was measured in the same manner as above, and the amount of permeate moisture before and after storage was measured, and the degree of deterioration resistance was calculated according to the following formula, and evaluated according to the following criteria. Preservation.

Resistance to deterioration = (the amount of permeate after storage / the amount of permeate before storage) × 100 (%)

5: The degree of deterioration resistance is 98% or more.

4: The deterioration resistance is 95% or more and less than 98%.

3: The degree of deterioration resistance is 90% or more and less than 95%.

2: The deterioration resistance is 80% or more and less than 90%.

1: The degree of deterioration resistance is less than 80%.

<summary>

As is understood from Table 1, the gas barrier film of the present invention was found to have excellent water vapor permeability and storage stability as compared with the gas barrier film of the comparative example.

From the above, it is understood that the gas barrier layer has a mixed region containing a transition metal of Group 5 and a non-transition metal (M1) of Group 12 to 14 at least in the thickness direction, and the glass transition temperature of the constituent material of the substrate is 150 ° C or higher. It is useful for providing a gas barrier film having high gas barrier properties and excellent productivity.

[Embodiment 2] "Production of Gas Barrier Films"

Gas barrier films 201 to 205 were produced in accordance with the following methods.

<Production of Gas Barrier Film 201> (1) Preparation of the substrate

On both sides of a 100 μm thick polyethylene terephthalate film (manufactured by TORAY Co., Ltd., LUMIRROR (registered trademark) U48, abbreviated as PET film), which is easily treated on both sides, a transparent hard film is formed by the following method. Coating 1 (back side) and transparent hard coat 2 (gas barrier layer forming side).

(formation of transparent hard coating)

The UV-curable resin was applied by wet coating on the back side of the PET film (the side opposite to the side on which the gas barrier layer was formed) so that the dry layer thickness was 0.5 μm (AICA Industrial Co., Ltd.) After the company's system, product number: Z731L), the formed coating film was dried at 80 ° C, and then hardened under high air mercury lamp with an irradiation energy of 0.5 J/cm ^{2 to} form a transparent hard coat layer 1 on the back side. .

Next, on the surface of the PET film (the surface on which the gas barrier layer is formed), a UV-curable resin "OPSTAR (registered trademark) Z7527" manufactured by JSR Co., Ltd. was used to wet the layer to a thickness of 2 μm. After coating by the coating method, it was dried at 80 ° C, and then hardened under air using a high-pressure mercury lamp at an irradiation energy of 0.5 J/cm ^{2 to} form a transparent hard coat layer 2 having a thickness of 2 μm on the surface side.

(2) Formation of gas barrier layer (Formation of a film containing a non-transition metal (M1))

A polyazoxide containing Si is used as the non-transition metal (M1), as described below, by coating. The modification method forms a film containing a non-transition metal (M1).

First, a dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) containing 20% by mass of perhydropolyazane (PHPS) and an amine-containing catalyst were mixed at a ratio of 4:1 (mass ratio). N, N, N', N'-tetramethyl-1,6-diaminohexane (TMDAH)) perhydropolyazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd. , NN120-20), and then used to adjust the dry film thickness of the dehydrated dibutyl ether When diluted, prepare a coating solution.

Next, the coating liquid was applied by a spin coating method so as to have a dry film thickness of 55 nm in a nitrogen atmosphere in a glove box, and dried at 80 ° C for 10 minutes.

Next, a sample containing a film containing a non-transition metal (M1) was placed in a vacuum ultraviolet irradiation apparatus shown in Fig. 4 of a Xe excimer lamp having a wavelength of 172 nm, and vacuum ultraviolet rays were applied under the conditions of an irradiation energy of 5.0 J/cm ² . Irradiation treatment. At this time, nitrogen gas and oxygen gas were supplied to the chamber, and the oxygen concentration in the irradiation environment was adjusted to 0.1% by volume. And the temperature of the set sample was set to 80 °C.

In the vacuum ultraviolet irradiation apparatus 100 shown in FIG. 4, reference numeral 101 denotes a device chamber, and nitrogen gas and oxygen gas are supplied to an appropriate amount from a gas supply port (not shown), and are exhausted from a gas discharge port (not shown). The portion substantially removes water vapor and maintains the oxygen concentration at a specific concentration. Symbol 102 is a Xe excimer lamp (excimer light intensity: 130 mW/cm ² ) having a double tube structure irradiated with vacuum ultraviolet light of 172 nm, and symbol 103 serves as a fixture for an excimer lamp of an external electrode. Symbol 104 is a sample stage. The sample stage 104 reciprocates horizontally at a specific speed in the apparatus chamber 101 by a moving mechanism (not shown). Further, the sample stage 104 can be maintained at a specific temperature by a heating mechanism (not shown). Reference numeral 105 is a sample in which a polyazirane coating layer is formed. When the sample stage is horizontally moved, the height of the sample stage is adjusted so that the shortest distance between the surface of the coating layer of the sample and the surface of the excimer lamp tube is set to 3 mm. Reference numeral 106 is a light shielding plate, and the coating layer of the sample is not irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 102.

The energy applied to the surface of the sample coating layer in the vacuum ultraviolet light irradiation step was measured using a UV-integrated light meter manufactured by Hamamatsu Photonics Co., Ltd.: C8026/H8025 UV POWER METER using a 172 nm sensor head. During the measurement, the shortest distance between the Xe excimer lamp face and the measuring surface of the sensor head is set to 3 mm, the sensor head is placed at the center of the sample stage 104, and the environment inside the device chamber 101 is vacuum ultraviolet light. Nitrogen gas and oxygen gas were supplied so as to have the same oxygen concentration in the irradiation step, and the sample stage 104 was moved at a speed of 0.5 m/min. Before the measurement, in order to stabilize the illuminance of the Xe excimer lamp 102, an aging time of 10 minutes was set after the Xe excimer lamp was turned on, and then the sample stage was moved to start measurement.

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

(Formation of a film containing a transition metal)

On the above-mentioned film containing non-transition metal (M1), by gas phase method. Sputtering (magnetron sputtering device manufactured by CANON ANELVA, Form EB1100) forms a film containing a transition metal.

A commercially available metal Nb target was used as a target, and a mixed gas of Ar and O ₂ was used as a process gas, and a film was formed to have a thickness of 9 nm by DC sputtering. The sputtering power supply was set to 5.0 W/cm ² and the film formation pressure was set to 0.4 Pa. Further, in the film formation conditions, the oxygen partial pressure was set to 12%. In addition, film formation was performed in advance using a glass substrate, and in the film formation conditions, data on the thickness change of the film formation time was taken, and the thickness of the film formed per unit time was calculated, and then the film formation time was set so as to be the set thickness.

From the above, a gas barrier layer having a layer thickness of 64 nm was formed.

(3) XPS analysis of gas barrier layer

The XPS analysis was carried out in the same manner as in Example 1 with respect to the gas barrier layer formed by the above method.

(4) Calculation of oxygen deficiency index (2y+3z)/(a+bx) in the mixed region

The value of (2y + 3z) / (a + bx) in the thickness direction of the mixed region was calculated in the same manner as in the first embodiment.

<Production of Gas Barrier Films 202 to 204>

In the production of the gas barrier film 201, the gas barrier films 202 to 204 were produced in the same manner except that the substrate was changed to the one shown in Table 2.

PEN: Teijin Co., Ltd., TEONEX

PES: Sumitomo Chemical Co., Ltd. SUMIKA EXCEL4010GL30

PI: NEOPLEM manufactured by Mitsubishi Gas Chemical Co., Ltd.

<Production of Gas Barrier Film 205>

In the production of the gas barrier film 204, the gas barrier film 205 was produced in the same manner except that the target material in the case where the transition metal-containing film was formed was changed to a metal Ta target and the film thickness was 10 nm.

"Evaluation"

The water vapor transmission rate and the storage stability were evaluated in the same manner as in Example 1 for each of the gas barrier films produced.

The evaluation results are shown in Table 2.

<summary>

As is understood from Table 2, the gas barrier film of the present invention was found to have excellent water vapor permeability and storage stability as compared with the gas barrier film of the comparative example.

[Industrial availability]

The present invention is particularly preferably used for providing a gas barrier film having high gas barrier properties and excellent productivity.

1‧‧‧ gas barrier film

2‧‧‧Substrate

3‧‧‧ gas barrier

Claims (9)

A gas barrier film characterized by having a gas barrier layer on a substrate, wherein the gas barrier layer has a transition metal of Group 5 (M2) and a non-transition metal of Group 12-14 at least in a thickness direction In the mixed region of (M1), the glass transition temperature of the constituent material of the substrate is 150 ° C or higher. The gas barrier film according to claim 1, wherein the constituent material of the substrate has a glass transition temperature of 180 ° C or higher. The gas barrier film of claim 2, wherein the constituent material of the substrate is polyimine. The gas barrier film according to claim 1, wherein the gas barrier layer has a region containing a group 5 transition metal (M2) or a compound thereof as a main component a (hereinafter referred to as "A region") and contains 12 to 14 a non-transition metal (M1) or a compound thereof is a region of the main component b (hereinafter referred to as "B region"), and the mixed region is interposed between the A region and the B region, and the mixed region contains The compound of the main component a and the main component b described above. The gas barrier film according to claim 1, wherein when the composition of the mixing region is represented by the following chemical composition formula (1), at least a part of the mixing region satisfies the following relation (2), chemical composition formula (1): (M1)(M2) _x O _y N _z Relationship (2): (2y+3z)/(a+bx)<1.0 (except, where M1: non-transition metal, M2: transition metal, O: Oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, a: the maximum valence of M1, b: the maximum valence of M2). The gas barrier film of claim 1, wherein the aforementioned non-transition metal (M1) is ruthenium. An electronic device characterized by comprising the gas barrier film according to any one of claims 1 to 6. An electronic device according to claim 7, which has a resin layer of a content sub-point. An electronic device according to claim 7, which is provided with an organic electroluminescence element.