WO2017013980A1 - Gas barrier film - Google Patents

Abstract

The present invention addresses the problem of providing a gas barrier film that has excellent gas barrier properties and exceptional durability in high-temperature and high-humidity environments, specifically in terms of having exceptional adhesion between a gas barrier layer and a base material even when subjected to a high-temperature and high-humidity environment. This gas barrier film is characterized by including a laminate C in which a foundation layer A that contains a compound including a transition metal M1 and a gas barrier layer B that contains at least silicon (Si) and nitrogen (N) and that is formed in contact with the foundation layer A are laminated in the stated order, and is characterized in that when the thickness-direction composition of the laminate C is analyzed by XPS, the transition metal M1 and Si are present together in the interface region between the foundation layer A and the gas barrier layer B, a region D is present in which the value of the atomic ratio of the transition metal M1/Si is within the range of 0.11-9.0, and the thickness of the region D is at least 5 nm.

Description

Gas barrier film

The present invention relates to a gas barrier film. More specifically, the present invention relates to a gas barrier film having high gas barrier properties and excellent durability (interlayer adhesion) in a high temperature and high humidity environment.

In a flexible electronic device, in particular, a flexible organic electroluminescence (hereinafter abbreviated as organic EL) device, a gas barrier film is used as a substrate film or a sealing film. The gas barrier film used for these is required to have high gas barrier properties against moisture and oxygen.

Generally, a gas barrier film is manufactured by forming an inorganic barrier layer on a film by a vapor deposition method such as a vapor deposition method, a sputtering method, or a chemical deposition method (CVD method: Chemical Vapor Deposition). Silicon-containing compounds such as silicon oxide are widely used as the inorganic barrier layer, but silicon nitride is known to provide higher barrier properties than silicon oxide, and many studies have been made. Has been made.

In recent years, a manufacturing method in which a gas barrier layer is formed by irradiating energy to a barrier precursor layer formed on a substrate by a solution coating method has been studied. In particular, as a novel gas barrier layer deposition method, a coating liquid containing a silicon compound such as polysilazane is applied onto a substrate, and the applied polysilazane coating film is irradiated with vacuum ultraviolet light to constitute silicon oxide. A method for forming a gas barrier layer is proposed (see, for example, Patent Document 1).

The method described in Patent Document 1 is light in a range of 100 to 200 nm, which is called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”), which is larger than the interatomic bonding force in polysilazane. Use energy. As a result, by the action of only photons called photon processes, the oxidation reaction with active oxygen or ozone proceeds while directly breaking the atomic bonds, resulting in a silicon oxynitride composition at a relatively low temperature and high barrier properties. Has been attracting attention.

However, the gas barrier film produced by such a method is still insufficient as a barrier property. For example, the gas barrier film is at a level that can be used as a substrate of an organic EL device that requires a high gas barrier property. Not reached. In addition, since the adhesiveness between layers under high temperature and high humidity (hereinafter, also referred to as “adhesion”) is deteriorated, the durability is insufficient.

Specifically, a gas barrier layer formed by modifying polysilazane with excimer light has good gas barrier properties at a low temperature up to about 40 ° C., for example, at a high temperature and high humidity such as 85 ° C. and 85% RH. Under extremely harsh environments, it was found that even a gas barrier layer formed by this method deteriorates the gas barrier property with the passage of time. This is due to the fact that the adhesion between the gas barrier layer formed by modifying the base material and the polysilazane decreases due to storage in a high temperature and high humidity environment, and peeling occurs between the base material and the gas barrier layer. It is believed that there is.

Based on the above situation, there is a demand for the development of a gas barrier film for electronic devices having high gas barrier properties and excellent adhesiveness even in a high temperature and high humidity environment.

Special table 2009-503157

The present invention has been made in view of the above-mentioned problems and circumstances, and its solution is to have a high gas barrier property and durability in a high-temperature and high-humidity environment. Even so, it is to provide a gas barrier film having excellent adhesion between the gas barrier layer and the substrate.

As a result of examining the cause of the above-mentioned problem in order to solve the above-mentioned problem according to the present invention, the base layer A containing the compound containing the transition metal M1 and the base layer A are formed on the base material, It has a laminate C in which a gas barrier layer B containing at least silicon (Si) and nitrogen (N) is laminated in this order, and a transition metal is present in the interface region between the base layer A and the gas barrier layer B. A gas characterized in that M1 and Si coexist, the region D has a value of the atomic ratio of the transition metal M1 / Si within a specific range, and the thickness of the region D is 5 nm or more. It has been found that a gas barrier film having high gas barrier properties and excellent adhesion (adhesion) between the gas barrier layer and the substrate in a high temperature and high humidity environment can be obtained by the barrier film.

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

1. An underlayer A containing a compound containing a transition metal M1 and a gas barrier layer B formed in contact with the underlayer A and containing at least silicon (Si) and nitrogen (N) are formed on the substrate. A gas barrier film having a laminate C laminated in order,
When the composition distribution in the thickness direction of the laminate C is analyzed by the XPS method, the transition metal M1 and Si coexist in the interface region between the base layer A and the gas barrier layer B, and the transition metal M1 / Si. A gas barrier film comprising a region D having an atomic ratio value of 0.11 to 9.0 and a thickness of the region D of 5 nm or more.

2. The gas barrier film according to item 1, wherein the compound containing the transition metal M1 is a spherical particle.

3. The gas barrier property according to Item 1 or 2, wherein the transition metal M1 is at least one selected from niobium (Nb), zirconium (Zr), titanium (Ti), and iron (Fe). the film.

4. The gas barrier property according to any one of items 1 to 3, wherein the gas barrier layer B is a layer formed by applying a coating liquid containing polysilazane and drying the coating solution. the film.

5. 5. The gas barrier film according to item 4, wherein the coating liquid containing polysilazane used for forming the gas barrier layer B further contains an aluminum compound or a boron compound.

6. When the laminate C is analyzed by XPS method for the composition distribution in the thickness direction, the transition metal M2 and Si coexist in a region different from the region D, and the atomic ratio of the transition metal M2 / Si The ratio according to any one of Items 1 to 5, wherein the ratio E is within a range of 0.11 to 9.0, and the region E is not in contact with the region D. Gas barrier film.

7). When showing the film composition in the region E in SiM2 _x O _y N _z, gas barrier film as described in paragraph 6, characterized in that satisfies represented by the following formula (1).

Formula (1)
0 <(2y + 3z) / (a + bx) <1.0
[Wherein, a is the valence of Si. b is the maximum valence of the transition metal M2. ]
8). The gas barrier film according to Item 6 or 7, wherein the transition metal M2 is niobium (Nb) or tantalum (Ta).

According to the present invention, it is possible to provide a gas barrier film having high gas barrier properties and excellent adhesion between a gas barrier layer and a substrate in a high temperature and high humidity environment.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

As described above, the gas barrier film of the present invention is formed on a base material in contact with the base layer A containing the compound containing the transition metal M1, and at least silicon (Si) and nitrogen ( N) and the gas barrier layer B containing the laminate C in this order, and when the composition distribution in the thickness direction of the laminate C is analyzed by the XPS method, the base layer A and the gas In the interface region with the barrier layer B, there is a region D in which transition metal M1 and Si coexist and the atomic ratio of transition metal M1 / Si is in the range of 0.11 to 9.0. And the thickness of the said area | region D is 5 nm or more, and by setting it as the structure prescribed | regulated above, while achieving high gas-barrier property, the gas barrier at the time of preserve | saved in a high-temperature, high-humidity environment Dramatically improves adhesion between layer and substrate It can be.

The region D according to the present invention is formed by the component of the gas barrier layer B entering the surface recess of the underlayer A containing the compound containing the transition metal M1, preferably the compound containing the transition metal M1 that is a spherical particle. Is done.

It is presumed that the formation of the region D at the interface between the base layer A and the gas barrier layer B is a synergistic action of the following two effects as a mechanism for improving the adhesiveness.

The first effect is that the M1-OH structure that is considered to exist on the surface of the compound containing the transition metal M1 reacts with the Si—NH ₂ structure of the gas barrier layer B to form an M1-O—Si bond. This M1-O—Si bond is considered less susceptible to hydrolysis than the Si—O—Si bond, and is less likely to deteriorate under high temperature and high humidity than an underlayer containing general colloidal silica. Therefore, high adhesiveness can be obtained by this effect.

As a second effect, since the underlayer A has a concavo-convex structure with spherical transition metal M1 particles, the underlayer A and the gas barrier layer B are intricately in contact with each other. When the material constituting the gas barrier layer B enters the gaps between the particles of the formation A, the anchor effect appears. In addition, since the area of the interface where the underlayer A and the gas barrier layer B are in contact with each other is greatly increased from the projected area of the interface, the area for forming the M1-O—Si bond is also increased. It is estimated that the number of M1-O—Si bonds increased, and as a result, high adhesiveness could be realized.

Schematic sectional view showing an example of the configuration of the gas barrier film The schematic diagram which shows an example of a structure of the area | region D formed in a base layer and a gas barrier layer interface Graph for explaining an example of the element profile and region D when the composition distribution of Si and transition metal M1 in the thickness direction of the gas barrier film is analyzed by the XPS method Schematic sectional view showing an example of the configuration of a gas barrier film having a region E on the gas barrier layer Schematic sectional view showing an example of a vacuum ultraviolet irradiation apparatus applicable to the formation of a gas barrier layer according to the present invention

The gas barrier film of the present invention contains, on a base material, an underlayer A containing a compound containing a transition metal M1, and at least silicon (Si) and nitrogen (N) in contact with the underlayer A. It has a laminated body C in which a gas barrier layer B is formed and laminated, and when the composition distribution in the thickness direction of the laminated body C is analyzed by the XPS method, an interface region between the base layer A and the gas barrier layer B is formed. The transition metal M1 and Si coexist, and the value of the atomic ratio of the transition metal M1 / Si is in a specific range, and the region D has a layer thickness of 5 nm or more. This feature is a technical feature common to or corresponding to the claimed invention.

In the present invention, from the viewpoint that the effect intended by the present invention can be further expressed, it is possible for the compound containing the transition metal M1 to be a spherical particle, so that the region D can be efficiently formed, resulting in better adhesion. It is preferable at the point which can obtain property.

In addition, it is more effective due to the interaction with the constituent material of the gas barrier layer that the transition metal M1 is at least one selected from niobium (Nb), zirconium (Zr), titanium (Ti), and iron (Fe). It is preferable from the viewpoint that M1-O—Si bonds can be formed and excellent adhesiveness can be obtained even when stored in a high temperature and high humidity environment.

Further, it is preferable that the gas barrier layer B is a layer formed by applying a coating liquid containing polysilazane and drying it, because a high-quality gas barrier layer can be formed by simple means. .

Further, the gas barrier layer B is a layer formed by applying and drying a coating liquid containing polysilazane and an aluminum compound, or polysilazane and a boron compound, and the transition metal shown below is further formed thereon. When M2 is formed, the gas barrier property in the region E shown below can be further stabilized, which is preferable in terms of increasing production efficiency.

Further, when the laminate C is analyzed by XPS method for the composition distribution in the thickness direction, the transition metal M2 and Si coexist in a region different from the region D, and the transition metal M2 / Si When the ratio of atomic ratios is in the range of 0.11 to 9.0 and the region E is not in contact with the region D, or the composition in the region E is expressed by SiM2 _x O _y N _z Satisfying the condition represented by the above formula (1) is a region where the transition metal M2 and Si are stably combined as the region E, and it is difficult to be hydrolyzed, and higher gas barrier properties can be realized. Is preferable.

The transition metal M2 is niobium (Nb) or tantalum (Ta), which is a constituent material of the gas barrier layer and can form an effective M2-O—Si bond by interaction with Si. It is preferable in that excellent adhesiveness can be obtained even when stored in a high temperature and high humidity environment.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” 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. In the explanation of each figure, numerals in parentheses after the constituent elements indicate the symbols shown in each figure.

<Overall configuration of gas barrier film>
The gas barrier film of the present invention contains, on a base material, an underlayer A containing a compound containing a transition metal M1, and at least silicon (Si) and nitrogen (N) in contact with the underlayer A. One of the characteristics is that the gas barrier layer B is formed and the laminate C is laminated in this order.

Further, when the composition composition distribution in the thickness direction of the laminate C is analyzed, the transition metal M1 and Si coexist in the interface region between the base layer A and the gas barrier layer B, and the transition metal M1 / Si A region D having a thickness of 5 nm or more having an atomic ratio value in a range of 0.11 to 9.0 is provided.

The “gas barrier film” as used in the present invention has a water vapor permeability (abbreviation: WVTR, temperature: 38 ° C., relative humidity (RH): 100%) measured by a method according to JIS K 7129-1992. It means that the film is 1.0 (g / m ² · 24 h) or less.

The water vapor transmission rate can be determined by, for example, measuring with a water vapor transmission rate measuring device (trade name: Permatran, manufactured by Mocon) in an atmosphere of 38 ° C. and 100% RH.

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

In FIG. 1, a gas barrier film (1) has a base layer (3) containing a compound containing a transition metal M1 as a first constituent layer on a substrate (2), on which As the second constituent layer, a gas barrier layer B (4) containing at least silicon (Si) and nitrogen (N) is formed to constitute a laminate (C).

(Region D)
In the present invention, as shown in FIG. 1, the atomic ratio value of the transition metal M1 / Si is between the base layer A (3) and the gas barrier layer B (4) constituting the laminate (C). A region D having a layer thickness within a range of 0.11 to 9.0 and having a thickness of 5 nm or more is provided.

By taking the above-mentioned configuration defined in the present invention, the underlayer A (3) is composed of a compound containing the transition metal M1, preferably spherical particles containing the transition metal M1, and as a result, the underlayer A (3). The surface of the substrate has a concavo-convex structure, and a gas barrier layer B (4) is formed thereon, preferably by wet coating, so that the concavo-convex structure portion on the surface of the base layer A (3) is formed as described above. When the coating liquid for forming the gas barrier layer B enters, M1-OH present on the surface of the compound containing the transition metal M1 constituting the underlayer A (3) and Si— constituting the gas barrier layer B (4) NH ₂ reacts at the contact interface to form M1-O—Si bonds. This M1-O—Si bond, for example, Nb—O—Si bond, Zr—O—Si bond, Ti—O—Si bond, Fe—O—Si bond, etc. is added to the Si—O—Si bond. Compared to the structure in which the base layer contains colloidal silica and the like, it is less likely to be decomposed, so that it is less deteriorated in a high-temperature and high-humidity environment, and excellent adhesiveness can be maintained.

Furthermore, when the constituent components of the gas barrier layer enter the surface region of the underlying layer A having a concavo-convex structure, an anchor effect is exhibited, the contact area between the two is increased, and the M1-O—Si bond area is increased. Thereby, stronger adhesiveness can be obtained.

FIG. 2 is a schematic diagram showing an example of the configuration of the region D formed at the interface between the base layer and the gas barrier layer.

In the partial structure of the gas barrier film (1) shown in FIG. 2, an underlayer A (3) containing a compound containing a transition metal M1 is formed on a substrate (not shown). By applying the spherical particles as the compound, a concavo-convex structure is formed corresponding to the shape of the spherical particles constituting the base layer A (3), and the particle density is also particularly high in the surface region of the base layer A (3). It is low, and there is a gap between the particles. By forming a gas barrier layer B (4) containing silicon (Si) and nitrogen (N) on the base layer A (3) having such a structure by a wet coating method, A region having a thickness of 5 nm or more in which the value of the atomic ratio of the transition metal M1 / Si is in the range of 0.11 to 9.0 when the gas barrier layer forming coating solution enters the concavo-convex structure portion. D can be formed.

The thickness of the region D according to the present invention is 5 nm or more, preferably 5 to 30 nm, and more preferably 8 to 20 nm. If it is in the range prescribed | regulated above, favorable gas-barrier property and adhesiveness can be made compatible.

In the present invention, as a specific means for controlling the region D to a desired thickness, for example, a compound containing the transition metal M1 used for forming the underlayer, more specifically, the particle size of the spherical particles, and the like are appropriately selected. In addition to the method for controlling the degree of unevenness on the surface, the density of the compound containing the transition metal M1 and the mass ratio of the compound containing the transition metal M1 and the binder for forming the underlayer can be appropriately set. it can.

The thickness of the region D is preferably changed in relation to the degree of unevenness of the surface depending on the compound constituting the underlayer A (3), more specifically, the particle size of the spherical particles.

If the unevenness of the underlayer A (3) is too small, the first effect and the second effect described in the above estimation mechanism cannot be sufficiently exhibited, and the adhesiveness may be insufficient. On the other hand, if the number of irregularities of the underlayer A is excessive or too deep, the surface roughness of the gas barrier layer B (4) becomes rough, and the protrusion (uneven structure) of the underlayer A (3) is provided thereon. It becomes impossible to coat with the gas barrier layer B (4), and as a result, it becomes difficult to obtain sufficient gas barrier properties.

Therefore, the degree of surface unevenness of the foundation layer A (3) can be quantified by measuring the difference in thickness of the foundation layer A (3) from the cross-sectional TEM image. The height difference of the underlayer A (3) is preferably in the range of 5 to 30 nm, more preferably in the range of 8 to 20 nm when measured in the range of the cross-sectional TEM image length of 1.0 μm. It is.

<Composition analysis by XPS and measurement of thickness of region D>
In the region D according to the present invention, when the composition distribution in the thickness direction of the laminate C is analyzed by the XPS method, the transition metal M1 and Si coexist in the interface region between the base layer A and the gas barrier layer B. The transition metal M1 / Si has an atomic number ratio in the range of 0.11 to 9.0 and a thickness of 5 nm or more.

Next, a method for measuring the region D by the XPS analysis method will be described.

The element concentration distribution (hereinafter also referred to as a depth profile) in the thickness direction of the laminate C according to the present invention is specifically a transition metal M1 distribution curve, a silicon distribution curve, an oxygen distribution curve, a nitrogen distribution curve, and carbon. A distribution curve or the like is performed by using both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon to sequentially expose the inside from the surface of the laminate C. It can be created by so-called XPS depth profile measurement that analyzes the composition. 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 the element distribution curve with the horizontal axis as the etching time in this way, the etching time is roughly correlated with the distance from the surface of the gas barrier layer B (4) in the thickness direction of the laminate C in the layer thickness direction. Therefore, as the “distance from the surface of the gas barrier layer B (4) in the thickness direction of the laminate C”, the gas calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface of the barrier layer can be employed. 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).

Hereinafter, an example of specific conditions of XPS analysis applicable to the present invention will be shown.

・ Analyzer: QUANTERASXM 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 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. Data processing uses MultiPak manufactured by ULVAC-PHI. The analyzed elements were silicon (Si), transition metal M1, oxygen (O), nitrogen (N), and carbon (C).

From the obtained data, the composition ratio is calculated, and the range in which the transition metal M1 and Si coexist and the atomic ratio of the transition metal M1 / Si is in the range of 0.11 to 9.0 is obtained. This was defined as region D and its thickness was determined. The thickness of the region D represents the sputtering depth in XPS analysis in terms of SiO ₂ .

As described above, in the present invention, the thickness of the region D is 5 nm or more, preferably in the range of 5 to 30 nm, and more preferably in the range of 8 to 20 nm.

FIG. 3 shows a schematic graph of the element profile when the composition distribution of Si and the transition metal M1 in the thickness direction of the gas barrier film including the region D is analyzed by the XPS method.

FIG. 3 shows the elemental analysis of Si, M1, O, N, and C in the depth direction from the surface of the gas barrier film (left end of the graph), and the horizontal axis represents the sputter depth (film thickness: nm). Is a graph showing the Si and M1 content (atom%) on the vertical axis.

From the left side, the elemental composition of the gas barrier layer B (4), the elemental composition of the region D, and the elemental composition profile of the base layer A (3). It is within the range of 11 to 9.0.

<Constituent elements of gas barrier film>
The details of the substrate, the base layer A and the transition metal M1, the gas barrier layer B and the forming method, (region D), the region E, and the transition metal M2, which are constituent elements of the gas barrier film of the present invention, are described below. To do.

〔Base material〕
Examples of the substrate applicable to the gas barrier film of the present invention include a plastic film.

The plastic film is not particularly limited in material, thickness, and the like as long as it can hold the base layer A, the gas barrier layer B, and the like, and can be appropriately selected according to the purpose of use.

Examples of the plastic film applicable to the present invention include conventionally known plastic films. For example, JP-A-2013-226758, paragraphs (0124) to (0136), and International Publication No. 2013/002026. Examples thereof include plastic films described in paragraphs (0044) to (0047).

Preferable specific examples that can be used as the plastic film are polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like.

The substrate is not particularly limited as a shape such as a single wafer shape or a roll shape, but a roll shape that can be handled by a roll-to-roll method is preferable from the viewpoint of productivity.

The thickness of the substrate is appropriately selected depending on the application and is not particularly limited, but is typically in the range of 1 to 800 μm, preferably in the range of 5 to 500 μm, more preferably 10 to It is in the range of 200 μm.

The base material used in the present invention can be produced by a conventionally known general method. For example, a melt casting method for producing an unstretched substrate that is substantially amorphous and not oriented by melting a resin as a material with an extruder, extruding with an annular die or a T-die, and quenching, A solution casting method or the like in which a resin is dissolved in a solvent to prepare a dope, and then the dope is cast on a metal support and dried to produce a substrate, or the like can be used. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

At least on the side of the substrate on which the base layer A and the gas barrier layer are provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, can be performed. Preferably, it is more preferable to combine the above treatments as necessary.

[Underlayer A]
The underlayer A according to the present invention is a layer containing a compound containing at least a transition metal M1. Further, the transition metal M1 constituting the compound is preferably at least one selected from niobium (Nb), zirconium (Zr), titanium (Ti), and iron (Fe).

(Transition metal M1)
The transition metal M1 applied to the formation of the underlayer A according to the present invention refers to a Group 3 element to a Group 12 element. As the transition metal M1 according to the present invention, 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, Examples include Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, and Au.

Among them, Ti, Ce, Nb, Fe, Zr, La, and Nd are preferable, and at least one selected from Nb, Zr, Ti, and Fe that can obtain a compound having good transparency is preferable, and particularly preferable. Is Nb or Zr.

Although it does not specifically limit as an aspect of the compound containing the transition metal M1 which concerns on this invention, For example, it contains in the state of compounds, such as the oxide, nitride, carbide, oxynitride, or oxycarbide of the transition metal M1 Is mentioned. Among these, from the viewpoint of more effectively suppressing oxidation, the transition metal M1 is preferably contained in the underlayer A as an oxide. The transition metal M1 applied to the underlayer A may be used alone or in combination of two or more.

(Shape of compound containing transition metal M1)
One preferred embodiment of the compound containing the transition metal M1 according to the present invention is to have a particle shape.

The particle shape may be any shape such as a spherical shape, a spindle shape, and an indeterminate shape, but is preferably a spherical particle from the viewpoint that a desired uneven structure can be stably formed on the surface of the underlayer. In the present invention, the spherical particles have a major axis / minor axis ratio value (aspect ratio) in the range of 1.00 to 1.50, preferably in the range of 1.00 to 1.20. More preferably, it is in the range of 1.00 to 1.10.

The particle size of the compound containing the transition metal M1 is preferably in the range of 5 to 50 nm as the major axis, and more preferably in the range of 10 to 30 nm. Within this range, an appropriate uneven structure can be formed without forming coarse protrusions on the surface of the underlayer A.

(Compound containing transition metal M1)
In the present invention, the compound containing the transition metal M1 can be obtained as a commercial product. For example, as the nanoparticle dispersion of the transition metal oxide, the following ultrafine oxide sol can be mentioned.

The ultrafine oxide sols listed below are all manufactured by Taki Chemical Co., Ltd.

<TiO ₂ >
Tynock A-6 (trade name, component = TiO ₂ , secondary particle size = 20 nm, pH = 12)
Tynoch M-6 (trade name, component = TiO ₂ , secondary particle size = 10 nm, pH = 3)
Tynock AM-15 (trade name, component = TiO ₂ , secondary particle size = 20 nm, pH = 4)
Tynock CZP-223 (trade name, component = TiO ₂ , secondary particle size = 20 nm)
Tynoc RA-6 (trade name, component = TiO ₂ , secondary particle size = 35 nm, pH = 10)
etc,
<CeO ₂ >
Nidoral B-10 (trade name, component = CeO ₂ , secondary particle size = 20 nm, pH = 8)
Niedral P-10 (trade name, component = CeO ₂ , secondary particle size = 20 nm, pH = 7)
etc,
<Nb ₂ O ₅ >
Viral Nb-G6000 (trade name, component = Nb ₂ O ₅ , secondary particle size = 15 nm, pH = 8), etc.
<Fe ₂ O ₃ >
Viral Fe-C10 (trade name, component = Fe ₂ O ₃ , secondary particle size = 6 nm, pH = 7), etc.
<ZrO ₂ >
Viral Zr-C20 (trade name, component = ZrO ₂ , secondary particle size = 40 nm, pH = 7), etc.
<La ₂ O ₃ >
Viral La-C10 (trade name, component = La ₂ O ₃ , secondary particle size = 40 nm, pH = 8), etc.
<Nd ₂ O ₃ >
Examples include viral Nd-C10 (trade name, component = Nd ₂ O ₃ , secondary particle size = 20 nm, pH = 9).

The following zirconium oxide (ZrO ₂ ) sol (Nanouse (registered trademark) ZR series) is also commercially available from Nissan Chemical Industries.

ZR-30BS (particle size = 63 nm, pH = 9.8)
ZR-30BFN (particle size = 14 nm, pH = 7.2)
ZR-20AS (particle size = 42 nm, pH = 3.8)
Etc.

(binder)
In forming the underlayer A according to the present invention, a binder can be used together with the compound containing the transition metal M1 described above.

Examples of binders applicable to the formation of the underlayer A include diene (co) polymers such as polystyrene, polypropylene, polybutadiene, polyisoprene, and ethylene-butadiene copolymer, styrene-butadiene copolymer, and methyl methacrylate-butadiene. Copolymer, synthetic rubber such as acrylonitrile-butadiene copolymer, polymethyl methacrylate, methyl methacrylate- (2-ethylhexyl acrylate) copolymer, methyl methacrylate-methacrylic acid copolymer, methyl acrylate- (N-methylolacrylamide) Copolymers, (meth) acrylic (co) polymers such as polyacrylonitrile, polyvinyl acetate, vinyl acetate-vinyl propionate copolymers, vinyl ester (co) polymers such as vinyl acetate-ethylene copolymers, acetic acid Bi Le - (2-ethylhexyl acrylate) copolymers, polyvinyl chloride, polyvinylidene chloride, polystyrene and copolymers thereof.

(Formation method of base layer A)
In the present invention, as a method for forming the underlayer A on the substrate, for example, in addition to the compound containing the transition metal M1 and the binder, a solvent, a surfactant, and the like are added to form a coating solution for forming the underlayer A. After preparation, known spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method, etc. The base layer A can be formed by coating on a substrate by a wet coating method and drying and removing a solvent, a diluent and the like.

The thickness of the underlying layer A after drying is not particularly limited, but is in the range of 20 to 500 nm, preferably in the range of 20 to 200 nm, and more preferably in the range of 30 to 150 nm. .

[Gas barrier layer B]
The gas barrier layer B according to the present invention is not particularly limited as long as it is a layer containing at least silicon (Si) and nitrogen (N), but a preferred embodiment is that a coating liquid containing polysilazane is applied and dried. It is a layer formed.

Hereinafter, a method for forming the gas barrier layer B using polysilazane will be described.

The gas barrier layer B according to the present invention forms a gas barrier layer B and a region D on the base layer A according to the present invention by applying a coating liquid containing polysilazane by a known wet coating method and then performing a modification treatment. To do.

(Polysilazane)
The “polysilazane” used in the present invention is a polymer having a silicon (Si) -nitrogen (N) bond in the structure, and is a polymer that is a precursor of silicon oxynitride (SiON). What has the structure represented by these is used preferably.

In the general formula (1), 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, from the viewpoint of denseness of a film of the obtained gas barrier layer, perhydropolysilazane all of R ^1, R ² and R ³ are hydrogen atom (abbreviation: PHPS) are particularly preferred.

Polysilazane is also commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.

In addition, for details of polysilazane, for example, paragraphs (0024) to (0040) of JP2013-255910A, paragraphs (0037) to (0043) of JP2013-188942A, JP2013-2013A. No. 151123, paragraphs (0014) to (0021), JP 2013-052569 A, paragraphs (0033) to (0045), JP 2013-129557, paragraphs (0062) to (0075), The present invention can be applied with reference to the contents described in paragraphs (0037) to (0064) of JP2013-226758A.

(Method of forming a gas barrier layer using polysilazane)
In addition to polysilazane, the coating liquid for forming a gas barrier layer containing polysilazane contains a solvent and, if necessary, an additive element compound to be described later, and is wet-coated on the base layer A formed on the substrate. Form using the method.

Solvents used in the preparation of the coating solution for gas barrier layer formation include aprotic solvents; aliphatic hydrocarbons, alicyclic hydrocarbons, aromatics such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben Hydrocarbon solvents such as hydrocarbons; halogen hydrocarbon solvents such as methylene chloride and trichloroethane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Ethers such as cyclic ethers: For example, tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes) and the like can be mentioned.

The concentration of polysilazane in the coating liquid for forming a gas barrier layer is not particularly limited and varies depending on the thickness of the layer to be formed and the pot life of the coating liquid, but is preferably in the range of 1 to 80% by mass, more preferably 5 It is in the range of ˜50 mass%, more preferably in the range of 10˜40 mass%.

Any appropriate wet coating method can be employed as a method of applying the coating liquid containing polysilazane. Specifically, for example, spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, gravure printing method and the like can be mentioned. . After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the solvent contained in the coating film can be removed. Specific methods for forming the gas barrier layer include, for example, paragraphs (0058) to (0064) of JP2014-151571A, paragraphs (0052) to (0056) of JP2011-183773A, and the like. It can be adopted by reference.

(Modification process)
The modification treatment is treatment for imparting energy to polysilazane and converting part or all thereof to silicon oxide or silicon oxynitride.

As 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 plasma that can be converted at a low temperature, or a conversion reaction using ozone or ultraviolet light is preferable. Conventionally known methods can be used for plasma and ozone. In the present invention, a gas barrier layer is applied by applying a vacuum ultraviolet ray irradiation treatment in which a coating film of a polysilazane-containing coating solution of a coating method is provided on a substrate, and a modification treatment is performed by irradiating vacuum ultraviolet rays (VUV) having a wavelength of 200 nm or less. The method of forming B is particularly preferred.

The thickness of the gas barrier layer B is not particularly limited, but is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. Of the gas barrier layer, the entire gas barrier layer may be a modified layer, or a part of the gas barrier layer may be a partially modified layer that has been subjected to a modification treatment.

(Vacuum ultraviolet irradiation treatment)
In the gas barrier layer B according to the present invention, at least a part of the polysilazane is modified into silicon oxynitride in the step of irradiating the layer containing polysilazane with vacuum ultraviolet light (VUV).

In the VUV irradiation step in the present invention, the VUV illuminance on the coating surface received by the polysilazane-containing coating film that is the precursor of the gas barrier layer is preferably in the range of 30 to 200 mW / cm ² , and preferably 50 to 160 mW. More preferably within the range of / cm ² . By setting the illuminance of VUV to 30 mW / cm ² or more, the reforming efficiency can be sufficiently achieved, and by setting it to 200 mW / cm ² or less, the damage occurrence rate to the coating film can be suppressed to a very low level. And it is preferable from a viewpoint which can suppress the damage to a base material or the base layer A already formed.

Irradiation energy amount of VUV in the polysilazane coating film surface is preferably in the range of 200 ~ 10000mJ / cm ^2, and more preferably in a range of 500 ~ 5000mJ / cm ^2. By making the amount of irradiation energy of VUV 200 mJ / cm ² or more, the polysilazane layer can be stably reformed, and by setting it to 10000 mJ / cm ² or less, excessive modification is suppressed and formed. Occurrence of cracks in the gas barrier layer and thermal deformation of the base material and the underlayer A can be suppressed.

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.

Treatment by vacuum ultraviolet irradiation uses light energy having a wavelength 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 bonds the atoms to photons called photon processes. This is a method of forming a silicon oxide film in a relatively low temperature environment (about 200 ° C. or less) by causing an oxidation reaction with active oxygen or ozone to proceed while being directly cut by the action of only.

Oxygen is required for the reaction at the time of ultraviolet irradiation, but in the case of vacuum ultraviolet rays, if absorption by oxygen occurs, the efficiency in the vacuum ultraviolet irradiation process tends to decrease, so it is possible in the environment of vacuum ultraviolet irradiation. As long as the oxygen concentration and the water vapor concentration are low, it is preferable. That is, the oxygen concentration at the time of VUV irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, still more preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm.

At the time of VUV irradiation, it is preferable to use a dry inert gas as a gas that satisfies the irradiation atmosphere, and it is particularly preferable to use a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation environment and changing the flow rate ratio.

Details of these reforming treatments are described in, 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.

Two or more gas barrier layers may be laminated, and a gas barrier layer may be formed and laminated on a gas barrier layer formed by a plasma CVD method by a wet coating method using the polysilazane.

(Determining that the gas barrier layer is derived from polysilazane)
The gas barrier layer according to the present invention is preferably formed using polysilazane, particularly preferably perhydropolysilazane, as a precursor, but the gas barrier layer as the final product is a layer formed of polysilazane. It can be proved by analyzing by the following method.

In the present invention, an example in which perhydropolysilazane is applied as polysilazane will be described.

When the general composition of commercially available perhydropolysilazane is SiN _v H _w , v is 0.78 to 0.80. The precursor layer formed from perhydropolysilazane takes in moisture and oxygen in the forming atmosphere, releases ammonia and hydrogen, and changes its composition as shown in the following formulas (A) and (B).

In the process, one law of nitrogen is released, while the law that three oxygens are taken in is roughly followed. This is also true when the various reforming processes described above are performed. Therefore, when the composition of the gas barrier layer formed by coating from perhydropolysilazane is represented by SiO _x N _y , the relationship between x and y follows the following formula (C).

Formula (C)
y = 0.8−x / 3, x ≧ 0, y ≧ 0,
When the original composition is SiN _0.8 H _w , when the composition distribution in the thickness direction of the layer formed from perhydropolysilazane is analyzed by XPS, any composition at each measurement point in the thickness direction is the above This applies to the equation (there is a few percent error).

Therefore, when the composition distribution in the thickness direction of the layer containing Si is analyzed and indicated by SiO _x N _y , the measurement point of 80% or more of the thickness of the formed gas valley layer is obtained. If the composition has a y value in the range of ± 2% of (0.8−x / 3), it is possible to estimate that the layer is a gas barrier layer formed from perhydropolysilazane. Become.

(Additive elements)
In the present invention, the coating liquid for forming the gas barrier layer B contains an additive element (at least one element selected from the group consisting of elements of Group 2 to Group 14 of the long-period periodic table). It can be included. Examples of additive elements include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), magnesium (Mg) ), Tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), potassium (K ), Calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), germanium (Ge) and the like. .

The gas barrier layer according to the present invention is preferably formed by applying a coating liquid containing polysilazane and an aluminum compound, or polysilazane and a boron compound, and drying it.

In the gas barrier film of the present invention, as will be described later, the transition metal M2 and Si coexist at a position not in contact with the region D, and the value of the atomic ratio of the transition metal M2 / Si is 0. It is a preferred embodiment to have a region E in the range of .11 to 9.0.

When the region E is formed on the gas barrier layer B by applying the transition metal M2 by sputtering to form the region E, in the step of forming the region E from the formation of the gas barrier layer B by the transition metal M2, Depending on the environment in which the gas barrier film formed up to the barrier layer B is stored, the composition of the already formed gas barrier layer B may change. For example, the quality of the gas barrier film, for example, the gas barrier property is not stable due to a change in elemental composition such that nitrogen atoms are separated and oxygen atoms are taken in.

For the above problem, when an aluminum compound or a boron compound is used in combination with polysilazane when forming the gas barrier layer B, the composition change in a high-temperature and high-humidity environment after the formation of the gas barrier layer B is suppressed, and the stability is improved. In order to greatly improve, the quality (gas barrier property) when the sputtering process is performed on the gas barrier layer B with the compound containing the transition metal M2 in the subsequent process is stabilized, that is, the production stability is greatly improved.

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, and aluminum tri-n-butylate. Aluminum tri-sec-butyrate, aluminum ethyl acetoacetate diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum tert-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. it can.

Examples of the boron compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate and the like.

Of these, aluminum compounds are preferred. Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate). 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 (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.) 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 because by adding these compounds, polysilazane reacts with moisture and oxygen in the atmosphere, and violent oxidation is suppressed. When these compounds and polysilazane are mixed, the temperature is preferably raised to 30 to 100 ° C. and maintained for 1 minute to 24 hours with stirring.

The content of the additive element in the gas barrier layer is preferably in the range of 5 to 20 mol%, more preferably in the range of 5 to 10 mol% with respect to 100 mol% of the silicon (Si) content.

[Region E]
In the gas barrier film of the present invention, when the laminate C is analyzed for the composition distribution in the thickness direction by the XPS method, the transition metal M2 and Si coexist in different regions not in contact with the region D. In addition, it is preferable that the region E has a ratio of the number ratio of transition metal M2 / Si in the range of 0.11 to 9.0.

FIG. 4 is a schematic cross-sectional view showing an example of the configuration of a gas barrier film having a region E on the gas barrier layer.

As shown in FIG. 4, as a preferred embodiment of the gas barrier film (1) of the present invention, the substrate (2) has an underlayer (3) and a gas barrier layer (4). In the configuration having the region D between 3) and the gas barrier layer (4), the region E is further provided on the gas barrier layer (4). At this time, the region D and the region E are arranged at different positions.

The region E according to the present invention is formed by forming a layer containing the transition metal M2 on the gas barrier layer (4) formed from the coating liquid containing polysilazane by a vapor deposition method. It is preferable. As the vapor deposition method, physical vapor deposition is preferable, and sputtering is particularly preferable. Applicable sputtering methods include DC sputtering method, RF sputtering method, magnetron sputtering method, ion beam sputtering method and the like, and there are no particular restrictions on the method, but among them, a magnetic field is applied to the target side with a magnet. Magnetron sputtering, which forms and separates the plasma from the sample, is preferred.

(Transition metal M2)
The transition metal M2 applicable to the formation of the region E according to the present invention refers to a Group 3 element to a Group 12 element. As the transition metal M2 according to the present invention, 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, Examples include Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, and Au.

Of these, the transition metal M2 is preferably a metal having a lower redox potential than silicon. By setting the region to contain a transition metal compound having a lower oxidation-reduction potential than silicon, better gas barrier properties can be obtained. Specific examples of the metal having a lower redox potential than silicon include niobium, tantalum, barium, zirconium, titanium, hafnium, yttrium, lanthanum, cerium, and the like. These metals may be used alone or in combination of two or more. Among these, the gas barrier layer (4) in which the group 5 elements niobium, tantalum, and vanadium are formed in the lower region has a high oxidation suppressing effect, and thus can be preferably used. That is, a preferred embodiment of the present invention is a gas barrier film in which the transition metal M2 is at least one metal selected from the group consisting of vanadium, niobium and tantalum. Furthermore, from the viewpoint of optical properties, the transition metal in the transition metal compound is particularly preferably niobium (Nb) or tantalum (Ta) from which a compound with good transparency can be obtained.

The mode of the compound containing the transition metal M2 according to the present invention is not particularly limited, and for example, a compound such as an oxide, nitride, carbide, oxynitride, or oxycarbide of the transition metal M can be used. Among these, from the viewpoint of more effectively suppressing oxidation, it is preferable to use an oxide as the transition metal M2.

In the gas barrier film of the present invention, the action mechanism for improving the gas barrier property by forming the region E containing the transition metal M2 on the gas barrier layer is estimated as follows.

As in the present invention, the region E containing the transition metal M2 is formed on the gas barrier layer, whereby the amount of the transition metal M2 is gradually reduced from the region E to the gas barrier layer side. it can. By forming a region E in which the ratio of the number ratio of transition metal M2 / Si is within a range of 0.11 to 9.0, region E is a region where Si and transition metal M2 are bonded. It is presumed that the gas barrier properties were improved.

In the gas barrier film of the present invention, the gas barrier layer is a layer containing silicon (Si), and the transition metal M2 contained in the region E is a Group 5 metal (for example, V, Nb, Ta, etc.). ), The gas barrier property is remarkably improved. Although this mechanism is not clear, since Si and Group 5 metal atoms are likely to form a bond, since the transition metal M2 is activated, it is deep in the gas barrier layer containing Si. It is estimated that this is an effect due to the formation of a dense region E containing Si—Nb bonds at the interface. Nb and Ta are particularly preferable among Group 5 metals from the viewpoint of transparency.

In the composition analysis in the region E, the composition distribution can be obtained using the XPS method as in the composition analysis in the region D described above.

(Composition in region E)
Also, when showing the film composition in the region E according to the present invention in SiM2 _x O _y N _z, which satisfies the conditions is a preferred embodiment shown by the following formula (1).

Formula (1)
0 <(2y + 3z) / (a + bx) <1.0
In the above formula (1), a is the valence of Si. b is the maximum valence of the transition metal M2. However, when the gas barrier layer B has a configuration of Si + Al, a configuration of Si + B, or a configuration of Si + Al + B, a represents the valence of the mixture calculated by the valences of Si, Al, and B and the respective atomic ratios. To express.

The thickness of this region E is preferably 5 nm or more.

The condition that the region E satisfies the condition defined by the above formula (1) is that the oxygen deficiency composition of the composite oxide of the main constituent element (Si) and the transition metal (M2) of the gas barrier layer B exceeds a predetermined thickness. It represents that it is included.

As described above, the composition of the composite oxide as a main constituent element of the gas barrier layer B according to the present invention (Si) and transition metal (M2) is represented by SiM2 _x O _y N _z.

A is the valence of Si.

As is clear from this composition, the composite oxide may partially include a nitride structure. Here, the valence of the constituent element (Si) of the gas barrier layer 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 composite oxide (including a partly nitrided) has a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0.

As described above, most of the gas barrier layer B is composed of Si, and Al or B is a case where a small amount is added, and calculation is often performed using Si alone.

This formula means that the total number of bonds of the constituent elements (Si) and transition metal (M2) of the gas barrier layer and the total number of bonds of O and N are the same. In this case, the gas barrier layer Both the constituent element (Si) and the transition metal (M2) are bonded to either O or N.

In addition, in this invention, when 2 or more types are used together as a constituent element of a gas barrier layer, or when 2 or more types are used together as a transition metal (M2), the maximum valence of each element is set to each element. The composite valence calculated by weighted averaging with the existence ratio is adopted as the values of a and b of the “maximum valence”.

On the other hand, in the case of (2y + 3z) / (a + bx) <1.0, O and N bond hands with respect to the sum of bond hands of the constituent elements (Si) and transition metal (M2) of the gas barrier layer. This means that the total is insufficient, and this state is an “oxygen deficiency” of the composite oxide. In the oxygen deficient state, the remaining bonds of the constituent element (Si) and transition metal (M2) of the gas barrier layer have the possibility of bonding to each other, and the constituent element (Si) and transition metal of the gas barrier layer When the metals of (M2) are directly bonded to each other, a denser and higher density structure is formed than when the metals are bonded via O or N, and as a result, the gas barrier property is considered to be improved.

<Other functional layers of gas barrier film>
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)
On the surface of the base material on the side on which 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, an anchor coat layer may be disposed together with the base layer according to the present invention. Good.

As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, 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. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 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 base material together with the base layer according to the present invention. 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 is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays 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 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, ie, 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 coat 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 Coat, 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 silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

The formation method of 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, 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, an appropriate resin or additive may be used in any of the hard coat layers in order to improve the film formability and prevent 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.

(Semiconductor nanoparticle layer)
The gas barrier film of the present invention can be used as a component for a wavelength conversion sheet called a so-called QD sheet in combination with a semiconductor nanoparticle layer.

The semiconductor nanoparticle layer can be provided mainly on the upper surface side of the region E, and is configured to contain semiconductor nanoparticles and an ultraviolet curable resin.

Two or more semiconductor nanoparticle layers may be provided. In this case, it is preferable that semiconductor nanoparticles having different emission wavelengths are contained in each of the two or more semiconductor nanoparticle layers.

The semiconductor nanoparticle layer contains semiconductor nanoparticles. That is, the semiconductor nanoparticles are contained in the coating solution for forming the semiconductor nanoparticle layer.

A semiconductor nanoparticle is a particle of a predetermined size that is composed of a crystal of a semiconductor material and has a quantum confinement effect, and is a fine particle having a particle diameter of about several nanometers to several tens of nanometers. The quantum dot effect shown below Means what can be obtained.

For matters relating to the semiconductor nanoparticles, for example, JP 2012-133158 A, 2012-169460, 2014-078381, 2015-099636, 2015-103728, 2015-127362. The contents described in the gazette and the like can be referred to.

《Electronic device》
The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, this invention can provide the electronic device containing the gas barrier film of this invention, and an electronic device main body.

Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and the sun. A battery (PV) etc. can be mentioned. 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.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. In the examples, “%” is used, but “mass%” is indicated unless otherwise specified.

Example 1
<< Preparation of base material with laminated base layer >>
[1. Preparation of coating solution for underlayer formation]
(Preparation of coating solution U1)
As the transition metal M1 compound, Tynoch RA-6 (secondary particle size: about 35 nm) manufactured by Taki Chemical Co., Ltd., which is an aqueous dispersion of titanium oxide particles, was used. Further, a soap-free acrylic emulsion AE986B (particle size: about 60 nm, Tg: 2 ° C.) manufactured by Etec Co., Ltd. was used as a binder. As a surfactant, Surfynol 465 manufactured by Air Products was used. The transition metal M1 compound / binder / surfactant was mixed at a mass ratio of 75.0 / 24.8 / 0.2 as a solid content ratio, and further diluted with pure water to obtain a solid content of 3.0 mass%. The coating liquid U1 was prepared.

(Preparation of coating solution U2)
Similar to the preparation of the coating liquid U1 except that as the transition metal M1 compound, Viral Nb-G6000 (secondary particle size: about 15 nm) manufactured by Taki Chemical Co., Ltd., which is an aqueous dispersion of niobium oxide particles, was used. Thus, a coating liquid U2 having a solid content of 3.0% by mass was prepared.

(Preparation of coating solution U3)
As the transition metal M1 compound, a bimetallic Fe-C10 (secondary particle size: about 6 nm) manufactured by Taki Chemical Co., Ltd., which is an aqueous dispersion of iron oxide particles, is used, and the transition metal M1 compound / binder / surfactant is used. The coating liquid U3 having a solid content of 3.0% by mass was prepared in the same manner as the coating liquid U1 except that the solid content was 72.0 / 26.8 / 0.2.

(Preparation of coating solution U4)
The preparation of the coating liquid U1 is the same as that for the transition metal M1, except that an aqueous dispersion of zirconium oxide particles, Viral Zr-C20 (secondary particle size: about 40 nm) manufactured by Taki Chemical Co., Ltd., is used. Thus, a coating liquid U4 having a solid content of 3.0% by mass was prepared.

(Preparation of coating solution U5)
As the transition metal M1, a nano-use ZR-30BS (particle diameter: about 63 nm) manufactured by Nissan Chemical Co., which is an aqueous dispersion of zirconium oxide particles, was used in the same manner as in the preparation of the coating liquid U1, A coating liquid U5 having a solid content of 3.0% by mass was prepared.

(Preparation of coating solution U6)
As a compound that is a non-transition metal, except that Snowtex 20L (particle diameter: about 50 nm) manufactured by Nissan Chemical Co., Ltd., which is an aqueous dispersion of silicon oxide particles, was used, the same as in the preparation of the coating solution U1, A coating liquid U6 having a solid content of 3.0% by mass was prepared.

(Preparation of coating solution U7)
Zirconium tetraisopropoxide and titanium tetraisopropoxide were used as the transition metal M1 compound. Zirconium tetraisopropoxide / titanium tetraisopropoxide as a solid content was mixed at a mass ratio of 90.0 / 10.0, and further diluted with isopropyl alcohol to obtain a coating liquid U7 having a solid content of 5.0 mass%. Prepared.

(Preparation of coating solution U8)
As the transition metal M1 compound, SZR-K (particle diameter: about 5 nm) manufactured by Sakai Chemical Industry Co., Ltd., which is a methyl ethyl ketone dispersion of zirconium oxide particles, was used. Polymerizable compound 1 (pentaerythritol acrylate, trade name: A-TMM-3, manufactured by Shin-Nakamura Chemical Co., Ltd.), polymerizable compound 2 (isocyanuric acid ethylene oxide modified acrylate, trade name: A-9300, Shin-Nakamura Chemical Co., Ltd.) Manufactured), a polymerization initiator (IRGACURE184, manufactured by Ciba Japan Co., Ltd.), and a surfactant (PF-6320, manufactured by OMNOVA SOLUTIONS) were used. Zirconium oxide particles / polymerizable compound 1 / polymerizable compound 2 / polymerization initiator / surfactant are mixed at a mass ratio of 40.0 / 47.0 / 10.0 / 2.8 / 0.2 as a solid content. Further, this was diluted with propylene glycol monomethyl ether to prepare a coating liquid U8 having a solid content of 20.0% by mass.

[2. Preparation of substrate with base layer]
(Substrate F0)
As a base material (resin base material), a 125 μm thick polyester film (Cosmo Shine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.) that was easily bonded on both surfaces was used as a base material F0 that had no base layer.

(Preparation of base material with base layer F1)
The prepared coating solution U1 (transition metal M1 = Ti) is applied to one side of the base material F0 under the condition that the solid content after drying is 0.1 g / m ^2, and then at 100 ° C. for 2 minutes. It dried and produced the base material F1 which has the base layer A containing Ti as a transition metal M1.

(Preparation of base material with base layer F2)
In the preparation of the base material with base layer F1, Nb is used as the transition metal M1 in the same manner except that the coating liquid U2 (transition metal M1 = Nb) is used instead of the coating liquid U1 (transition metal M1 = Ti). The base material F2 which has the base layer A to contain was produced.

(Preparation of base material with base layer F3)
In the production of the substrate F1 with the underlayer, Fe was used as the transition metal M1 in the same manner except that the coating liquid U3 (transition metal M1 = Fe) was used instead of the coating liquid U1 (transition metal M1 = Ti). The base material F3 which has the base layer A to contain was produced.

(Preparation of base material with base layer F4)
In the production of the base material F1 with the underlayer, Zr (as transition metal M1) was similarly obtained except that the coating liquid U4 (transition metal M1 = Zr) was used instead of the coating liquid U1 (transition metal M1 = Ti).
The base material F4 which has the base layer A containing a secondary particle diameter (about 40 nm) was produced.

(Preparation of base material with base layer F5)
In the production of the substrate F1 with the underlayer, Zr (as transition metal M1) was similarly obtained except that the coating liquid U5 (transition metal M1 = Zr) was used instead of the coating liquid U1 (transition metal M1 = Ti).
A base material F5 having an underlayer A containing a particle size of about 63 nm was produced.

(Preparation of base material with base layer F6)
In the production of the substrate F1 with the underlayer, the transition metal was similarly obtained except that the coating liquid U6 containing silicon oxide particles as a non-transition metal was used instead of the coating liquid U1 (transition metal M1 = Ti). The base material F6 which has the base layer A which does not contain M1 was produced.

(Preparation of base material with base layer F7)
The coating solution U7 (transition metal = Zr + Ti) prepared above, on one surface side of the substrate F0, after solid content after drying was coated with a condition to be 0.2 g / ^{m 2,} 10 minutes at 100 ° C. Dried. Next, details were similarly obtained except that the vacuum ultraviolet irradiation apparatus described in the formation of the gas barrier layer B described later was used and the vacuum ultraviolet irradiation condition was changed to 2.0 J / cm ² with respect to the gas barrier layer formation conditions. A base layer A was formed to prepare a base material F7 with a base layer.

(Preparation of base material with base layer F8)
The prepared coating solution U8 was applied on one surface side of the base material F0 under the condition that the solid content after drying was 2 g / m ^2, and then dried at 100 ° C. for 5 minutes. Then, under air, performing curing under conditions of irradiation energy 0.5 J / cm ² using a high-pressure mercury lamp to form the primary layer A, to prepare a base layer substrate with F8.

<< Production of gas barrier film >>
(Preparation of gas barrier layer forming coating solution S1)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials Co., Ltd., trade name: NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1, 6-diaminohexane (abbreviation: TMDAH)) and a 20% by mass dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) in a ratio of 4: 1 (mass ratio). Further, the coating solution S1 for gas barrier layer formation was prepared by diluting with dibutyl ether so that the solid concentration was 5% by mass. The gas barrier layer forming coating solution S1 was prepared in a glove box.

(Preparation of gas barrier film 1-1)
On the base material F0 which does not have the prepared underlayer A, coating is performed using the prepared coating solution S1 for gas barrier layer under the condition that the film thickness after drying is 150 nm by spin coating. And dried at 80 ° C. for 2 minutes.

Next, with respect to the dried perhydropolysilazane-containing layer, the vacuum ultraviolet irradiation device (10) shown in FIG. 5 having an Xe excimer lamp with a wavelength of 172 nm was used, and the irradiation condition of vacuum ultraviolet rays was 4.0 J / cm ² . Vacuum ultraviolet irradiation treatment was performed with the amount of irradiation energy. At this time, the irradiation atmosphere of vacuum ultraviolet rays was replaced with nitrogen gas, and the oxygen concentration was set to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C. In this way, the perhydropolysilazane-containing layer was modified to form a gas barrier layer B, and a gas barrier film 1-1 was produced.

In the vacuum ultraviolet irradiation apparatus (10) shown in FIG. 5, reference numeral 11 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 12 denotes an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm ² ) having a double tube structure that irradiates 172 nm vacuum ultraviolet rays, and reference numeral 13 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 14 denotes a sample stage. The sample stage 14 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 11 by a moving means (not shown). The sample stage 14 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 15 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 16 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 surface of the sample coating layer in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating photometer (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics. In the measurement, the sensor head is placed in the center of the sample stage (14) 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 (11) is Nitrogen and oxygen were supplied so as to obtain the same oxygen concentration as in the vacuum ultraviolet irradiation step, and the sample stage (14) was moved at a speed of 0.5 m / min, and measurement was performed. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp (12), an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the measurement was started by moving the sample stage (14).

Based on the irradiation energy obtained by this measurement, the moving speed of the sample stage (14) was adjusted to adjust the irradiation energy amount to 4.0 J / cm ² . The vacuum ultraviolet irradiation was performed after aging for 10 minutes.

(Production of gas barrier films 1-2 to 1-9)
In the production of the gas barrier film 1-1, a gas was produced in the same manner except that the substrates F1 to F8 having the prepared underlayer A were used instead of the substrate F0 not having the underlayer A. Barrier films 1-2 to 1-9 were produced.

<Evaluation of gas barrier film>
About each produced said gas-barrier film, each following measurement and evaluation were performed.

[Measurement of surface irregularities of the underlayer]
About each produced said sample, the cross-sectional TEM image was image | photographed and the height difference in the thickness direction of the base layer A was measured. The cross-sectional TEM image was measured within the range of 1.0 μm as the length of the interface between the base layer A and the gas barrier layer B. For one sample, five images for observation were taken at an arbitrary location, the maximum value of the height difference was measured for each image, and the average value of the five images was obtained. In addition, when the surface unevenness | corrugation of Table 1 is "0", it shows that the unevenness | corrugation in the surface could not be measured substantially.

However, in the above measurement, changes in gentle irregularities with a period exceeding 200 nm, which were caused by waviness of the base film, were excluded.

[Measurement of presence and thickness of region D]
The composition distribution profile in the thickness direction was measured on the surface side of the gas barrier film by XPS analysis. The XPS analysis conditions are as follows. The sample used for the analysis is a sample stored in an environment of 20 ° C. and 50% RH after the sample is prepared.

(XPS analysis conditions)
・ Device: QUANTERASXM 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, M1, O, N, and C.

From the obtained data, the transition metal M1 and Si coexist in the interface region between the base layer A and the gas barrier layer B, and the atomic ratio value of the transition metal M1 / Si is 0.11 to 9 A region in the range of 0.0 was defined as “region D”, and the presence or absence of region D and its thickness (nm) were measured.

[Evaluation of water vapor barrier properties]
Measurement was performed in an environment of 38 ° C. and 100% RH using a water vapor permeability measuring device PERMATRAN manufactured by MOCON. In addition, when it became a measurement result less than 0.005 g / m < ² > * day which is a measurement limit, it described as "less than a measurement limit" in Table 1.

[Evaluation of adhesion]
(Condition 1)
About each gas barrier film, the sample stored in 20 degreeC and 50% RH environment immediately after preparation was prepared.

Next, a 100-mass cross-cut test according to JIS K 5400 was performed on each sample. Each sample after the test was observed with an optical microscope, and the number of cells in which no peeling or chipping occurred substantially was counted out of 100 cells (the maximum number was 100).

(Condition 2)
About each gas-barrier film, the sample stored in 85 degreeC and 85% RH environment for 100 hours after sample preparation, and then the sample stored in 20 degreeC and 50% RH environment was prepared.

Each sample was subjected to a 100-mass cross-cut test according to JIS K 5400. The sample after the test was observed with an optical microscope, and the number of cells in which no peeling or chipping occurred substantially was counted out of 100 cells.

Table 1 shows the results obtained as described above.

As is clear from the results shown in Table 1, the gas barrier film of the present invention is superior to the comparative example in water vapor barrier properties (gas barrier properties), and can be bonded even when stored in a high temperature and high humidity environment. It can be seen that the adhesiveness is not deteriorated and good adhesiveness is maintained.

Example 2
<< Preparation of coating solution for gas barrier layer formation >>
(Preparation of gas barrier layer forming coating solution S2)
An aluminum compound-containing solution was prepared by diluting aluminum ethyl acetoacetate diisopropylate with dibutyl ether to a solid content concentration of 5% by mass.

Next, the gas barrier layer forming coating solution S1 described in Example 1 and the prepared aluminum compound-containing solution were mixed so that the value of the atomic ratio of Al / Si was 0.01 and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 2 hours, and then gradually cooled to room temperature. In this way, a coating liquid S2 for forming a gas barrier layer was prepared.

(Preparation of gas barrier layer forming coating solution S3)
A boron compound-containing solution was prepared by diluting triisopropyl borate with dibutyl ether so that the solid concentration was 5% by mass.

Next, the gas barrier layer-forming coating solution S1 described in Example 1 and the boron compound-containing solution prepared above were mixed so that the value of the B / Si atomic number ratio was 0.01 and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 2 hours, and then gradually cooled to room temperature. In this way, a coating liquid S3 for forming a gas barrier layer was prepared.

<< Production of gas barrier film >>
(Formation conditions for region E)
First, film formation conditions used for forming the region E in the gas barrier films 2-2 to 2-16 described below will be described collectively.

(Sputter deposition method and deposition conditions)
For the formation of the region E, a region E was formed on the gas barrier layer B using a magnetron sputtering device (Canon Anelva Co., Ltd. model: EB1100) as a vapor phase method / sputtering device.

As targets, the following targets were used, and Ar and O ₂ were used as process gases, and film formation was performed using a magnetron sputtering apparatus. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. In each film formation condition, the composition was adjusted by adjusting the oxygen partial pressure. It should be noted that the conditions of the composition are determined by adjusting the oxygen partial pressure by film formation using a glass substrate in advance, finding the condition that the composition near the depth of 10 nm from the surface layer becomes the target composition, and the condition is Applied. Regarding the film thickness, film thickness change data with respect to the film formation time is obtained in the range of 100 to 300 nm, the film formation time per unit time is calculated, and then the film formation time is set to the set film thickness. It was set.

<target>
T1: A silicon target containing no transition metal M2 was produced by the method described in Comparative Example 1 of the examples of JP2012-7218A. The target shape was a plate shape.

T2: A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb ₁₂ O ₂₉ .

T3: A commercially available Ta target was used.

<Film formation conditions>
T1-1: T1 was used as a target, and in the above XPS analysis, the oxygen partial pressure was adjusted so that the composition of the layer was SiO ₂ . The film formation time was set so that the film thickness was 15 nm.

T2-1: T2 was used as a target, and the oxygen partial pressure was 12%. The film formation time was set so that the film thickness was 15 nm.

T2-2: Performed in the same manner as T2-1 except that the film formation time was set so that the film thickness was 10 nm.

T2-3: Performed in the same manner as T2-1 except that the film formation time was set so that the film thickness was 5 nm.

T3-1: T3 was used as a target, and the oxygen partial pressure was 18%. The film formation time was set so that the film thickness was 15 nm.

(Preparation of gas barrier film 2-1)
In the production of the gas barrier film 1-1 described in Example 1, the thickness of the gas barrier layer after drying was changed to 80 nm, and the irradiation energy condition of vacuum ultraviolet rays was changed to 0.5 J / cm ² . In the same manner as described above, a gas barrier film 2-1 in which the sputter film formation was not performed and the region E was not formed was produced.

(Preparation of gas barrier film 2-2)
On the gas barrier layer of the gas barrier film 2-1 produced as described above, a region E not containing the transition metal M2 was formed under the film deposition condition T1-1 by sputtering. Here, after forming the gas barrier layer B and before performing sputter film formation, the sample formed up to the gas barrier layer B was stored in an environment of 20 ° C. and 50% RH.

(Production of gas barrier film 2-3 to 2-16)
In the production of the gas barrier film 2-2 produced above, the types of base layer-attached base materials, gas barrier layer formation conditions, and film formation conditions by sputtering in region E were changed to the combinations shown in Table 2 and Table 3. Except for the above, gas barrier films 2-3 to 2-16 were produced in the same manner.

<Evaluation of gas barrier film>
About each produced said gas-barrier film, each following measurement and evaluation were performed.

[Measurement of presence / absence and thickness of region D, presence / absence of region E and thickness]
In the same manner as in the method described in Example 1, the composition distribution profile in the thickness direction was measured on the surface side of the gas barrier film by XPS analysis.

The element composition ratio of each region was calculated from the obtained data, and the presence / absence of region D, the thickness of region D, the presence / absence of region E, and the thickness of region E were determined.

[When representing the composition of the region E in _{SiM2 x O y N z, (} 2y + 3z) / (a + bx) value calculation]
Calculation was performed using the XPS analysis data. Further, the values of x, y, z, a, and b at the measurement point where (2y + 3z) / (a + bx) is minimized were obtained.

Aluminum (Al) is added to the gas barrier layer forming coating solution S2 and boron (B) is added to the gas barrier layer forming coating solution S3, but in region E, Al and B are substantially detected. Was not.

[Evaluation of water vapor barrier properties]
(Condition A)
About each gas barrier film, the sample stored in 20 degreeC and 50% RH environment immediately after preparation was prepared.

The gas barrier film was measured under the conditions of 38 ° C. and 100% RH using a water vapor permeability measuring device manufactured by MOCON: PERMATRAN. When a measurement result less than 0.005 g / m ² · day, which is the measurement limit, was obtained, Table 3 describes “less than measurement limit”.

(Condition B)
Each gas barrier film sample was stored in an 85 ° C./85% RH environment for 24 hours after preparation, and then stored in a 20 ° C./50% RH environment.

The gas barrier film was measured under the conditions of 38 ° C. and 100% RH using a water vapor permeability measuring device manufactured by MOCON: PERMATRAN. When a measurement result less than 0.005 g / m ² · day, which is the measurement limit, was obtained, Table 3 describes “less than measurement limit”.

[Evaluation of adhesion]
In the same manner as the evaluation of adhesiveness described in Example 1, the adhesiveness was evaluated under conditions 1 and 2.

Tables 2 and 3 show the configuration of each gas barrier form and each evaluation result.

Table 2 shows the structures of the base material with the base layer, the gas barrier layer, and the region D of the gas barrier films 2-1 to 2-16, and Table 3 shows the gas barrier films 2-1 to 2-2. The characteristic value in the region E of −16 and each evaluation result are described.

As is clear from the results shown in Tables 2 and 3, the gas barrier film of the present invention further having the region E on the gas barrier layer can be stored in a high-temperature and high-humidity environment with respect to the comparative example. It can be seen that there is little deterioration in water vapor barrier properties (gas barrier properties), and even when stored in a high-temperature and high-humidity environment, there is no deterioration in adhesiveness, and good adhesiveness is maintained.

According to the present invention, it is possible to provide a gas barrier film that maintains excellent gas barrier properties even after being stored in a high-temperature and high-humidity environment, and has excellent adhesion to a base material. Films are susceptible to performance degradation due to chemical components in the air (for example, oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.). For example, organic EL elements, liquid crystal display elements (LCD) It can be applied to electronic devices such as thin film transistors, touch panels, electronic paper, and solar cells (PV).

1 Gas barrier film 2 Base material 3 Underlayer A
4 Gas barrier layer B
DESCRIPTION OF SYMBOLS 10 Vacuum ultraviolet irradiation apparatus 11 Apparatus chamber 12 Xe excimer lamp 13 Excimer lamp holder 14 Sample stage 15 Polysilazane compound coating layer forming sample 16 Light shielding plate C Laminate D Region D
E region E
M1 transition metal M1

Claims (8)

1. An underlayer A containing a compound containing a transition metal M1 and a gas barrier layer B formed in contact with the underlayer A and containing at least silicon (Si) and nitrogen (N) are formed on the substrate. A gas barrier film having a laminate C laminated in order,
   When the composition distribution in the thickness direction of the laminate C is analyzed by the XPS method, the transition metal M1 and Si coexist in the interface region between the base layer A and the gas barrier layer B, and the transition metal M1 / Si. A gas barrier film comprising a region D having an atomic ratio value of 0.11 to 9.0 and a thickness of the region D of 5 nm or more.
2. The gas barrier film according to claim 1, wherein the compound containing the transition metal M1 is a spherical particle.
3. The gas barrier property according to claim 1 or 2, wherein the transition metal M1 is at least one selected from niobium (Nb), zirconium (Zr), titanium (Ti), and iron (Fe). the film.
4. The gas barrier property according to any one of claims 1 to 3, wherein the gas barrier layer B is a layer formed by applying and drying a coating liquid containing polysilazane. the film.
5. The gas barrier film according to claim 4, wherein the coating liquid containing polysilazane used for forming the gas barrier layer B further contains an aluminum compound or a boron compound.
6. When the laminate C is analyzed by XPS method for the composition distribution in the thickness direction, the transition metal M2 and Si coexist in a region different from the region D, and the atomic ratio of the transition metal M2 / Si The gas according to any one of claims 1 to 5, wherein the gas has a region E that is within a range of 0.11 to 9.0 and is not in contact with the region D. Barrier film.
7. The gas barrier film according to claim 6, wherein when the film composition in the region E is expressed by SiM 2 _x O _y N _z , the condition represented by the following formula (1) is satisfied.
   Formula (1)
   0 <(2y + 3z) / (a + bx) <1.0
   [Wherein, a is the valence of Si. b is the maximum valence of the transition metal M2. ]
8. The gas barrier film according to claim 6 or 7, wherein the transition metal M2 is niobium (Nb) or tantalum (Ta).

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