WO2018021021A1

WO2018021021A1 - Gas barrier membrane, gas barrier film using same, electronic device using said gas barrier membrane or said gas barrier film, and production method for gas barrier membrane

Info

Publication number: WO2018021021A1
Application number: PCT/JP2017/025316
Authority: WO
Inventors: 森　孝博
Original assignee: コニカミノルタ株式会社
Priority date: 2016-07-28
Filing date: 2017-07-11
Publication date: 2018-02-01
Also published as: CN109477202A; JPWO2018021021A1

Abstract

The present invention provides a means with which a gas barrier membrane can satisfy both excellent bending properties and high water-vapor barrier properties in a high-temperature, high-humidity environment. The present invention relates to a gas barrier membrane having a region (a) that satisfies the following expression (1) and the following expression (2) when the composition is represented by M1M2_xN_y in the atomic composition distribution profile obtained when an XPS composition analysis is performed in the thickness direction. M1M2_xN_y Expression (1): 0.2 ≤ x ≤ 3.0 Expression (2): 0.6 ≤ y ≤ 1.4 x: Abundance ratio of transition metal M2 atoms with respect to non-transition metal M1 atoms y: Abundance ratio of nitrogen atoms with respect to non-transition metal M1 atoms

Description

Gas barrier film, gas barrier film using the same, electronic device using the same, and method for producing gas barrier film

The present invention relates to a gas barrier film, a gas barrier film using the same, an electronic device using the same, and a method for manufacturing the gas barrier film.

For flexible electronic devices, particularly flexible organic EL elements, a gas barrier film is used for sealing applications, and specifically, a gas barrier film having a gas barrier film is used as a substrate film or a sealing film. . A gas barrier film used for such applications is required to have a water vapor barrier property having a water vapor permeability (WVTR) of 10 ⁻⁶ g / (m ² · 24 h). Gas barrier films are known for both single-layer films and laminated films. For the purpose of achieving high barrier properties, typical gas barrier films currently being studied include, for example, silicon oxide films and silicon nitride films. And an alternate multilayer laminate film of a silicon nitride film and an organic film.

As a method for forming each of the gas barrier films and each film included in the gas barrier film having a laminated structure, a vapor deposition method such as a vapor deposition method, a sputtering method, or a CVD method is known. In recent years, a manufacturing method for forming a gas barrier film by applying energy to a precursor layer formed by applying a solution on a substrate has been studied. Among these, a method of forming an inorganic film having a thickness of 1 μm or more by a CVD method is generally used as a method for achieving a water vapor barrier property of 10 ⁻⁶ g / (m ² · 24 h) level. . However, an inorganic film having a thickness of 1 μm or more has a problem that cracks are generated at the time of bending, so that it is difficult to apply to the above-described flexible device. Further, the alternate multilayer laminated film tends to have a greater thickness due to its configuration. Accordingly, it is required to reduce the film thickness while maintaining high water vapor barrier properties.

Here, the alternate multilayer laminated film achieves an apparent low water vapor permeability, that is, a high water vapor barrier property by extremely delaying the time for water vapor to pass through the gas barrier layer due to the labyrinth effect formed by the laminated structure. It is thought that there is. For this reason, in the organic EL element using the alternating multilayer laminated film as a sealing application, the light emission failure such as the dark spot is not confirmed in the initial light emission inspection, but the dark spot is delayed after the accelerated test under the high temperature and high humidity environment. May occur. For this reason, a gas barrier film having a truly high water vapor barrier property is required instead of an apparent one in order to suppress a light emission failure that is not confirmed in the initial light emission inspection and to improve the durability of the element.

In the presence of such demands, technological development for forming an inorganic film having a truly high water vapor barrier property is underway. For example, JP 2012-149278 A includes a step of depositing a dry deposition film containing at least silicon atoms and nitrogen atoms on a substrate by a dry method, and then irradiating the film surface with light having a wavelength of 150 nm or less. A method for manufacturing a silicon-containing film is disclosed. According to the document, the silicon-containing film manufactured by this method, that is, the gas barrier film, has a large number of dense Si—N—Si bonds that form the basis of the Si ₃ N ₄ structure in the modified region, which is high. It is said to exhibit water vapor barrier properties and heat and moisture resistance.

However, the technique disclosed in Japanese Patent Application Laid-Open No. 2012-149278 achieves a water vapor barrier property at a level required for an organic EL element or the like at a thickness that exhibits excellent flexibility when applied to a flexible device. There is a problem that can not be.

Therefore, an object of the present invention is to provide means capable of achieving both excellent flexibility and high water vapor barrier property in a high temperature and high humidity environment in a gas barrier film.

The above-mentioned problem of the present invention can be solved by the following means.

The first aspect of the present invention is:
In the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction, a region satisfying the following formula (1) and the following formula (2) when the composition is represented by M1M2 _x N _y (a) It is a gas barrier film | membrane which has.

The second aspect of the present invention is:
A method for producing a gas barrier film, comprising forming a non-transition metal M1 containing layer and a transition metal M2 containing layer so as to contact each other,
In the thickness direction, it has a region (A) containing the non-transition metal M1 as the main component of the metal element and a region (B) containing the transition metal M2 as the main component of the metal element,
The region (A) and the region (B) are in contact with each other,
In the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction of the gas barrier film, the following formula (1) and the following formula (2) are satisfied when the composition is represented by M1M2 _x N _y A method for manufacturing a gas barrier film having a region (a) to be processed.

It is a typical graph for demonstrating an element profile and a mixed area | region when the composition distribution of the non-transition metal M1 and the transition metal M2 in the gas barrier film | membrane which concerns on one Embodiment of this invention is analyzed by XPS method. It is a cross-sectional schematic diagram which shows the laminated structure formed in the manufacturing method of the gas barrier film | membrane which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram which shows the laminated structure formed in the manufacturing method of the gas barrier film | membrane which concerns on other embodiment of this invention. It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus which can be used for formation of the gas barrier film which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram of the ultraviolet irradiation apparatus used in the Example.

Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In this specification, “X to Y” indicating a range means “X or more and Y or less”. In the present specification, unless otherwise specified, measurement of operation and physical properties is performed under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

In addition, the dimensional ratio of the drawings is exaggerated for convenience of explanation and may be different from the actual ratio. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

<Gas barrier film>
The gas barrier film according to the first aspect of the present invention has the following formula (1) when the composition is represented by M1M2 _x N _y in the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction. ) And the region (a) satisfying the following formula (2).

In the present specification, “the composition is indicated by M1M2 _x N _y ” means that the composition is indicated by focusing only on the non-transition metal M1 atom, the transition metal M2 atom and the nitrogen atom (N) in the existing atoms. Meaning, the region (a) may contain atoms other than these.

According to the first aspect of the present invention, it is possible to provide means capable of achieving both excellent flexibility and high water vapor barrier property in a high temperature and high humidity environment in the gas barrier property film. In addition, the water vapor barrier property in the high temperature and high humidity environment mentioned here means that water vapor permeation is suppressed at an extremely high level even in an accelerated test, that is, the water vapor barrier property of the gas barrier film is remarkably high. It also indicates that. Moreover, the flexibility here means that a high water vapor barrier property in a high temperature and high humidity environment is maintained even during bending.

The inventor presumes the mechanism by which the problem is solved by the above configuration as follows. First, the gas barrier film according to the first embodiment of the present invention includes a region (a) in which M1M2 _x N _y has a specific composition in the mixed region. Due to the existence of such a mixed region, the composition changes continuously or stepwise in the thickness direction of the gas barrier film. Therefore, the mixed region can suppress stress concentration, and an excellent flexibility of the gas barrier film is realized. In addition, although the mechanism of the high water vapor barrier property in a high temperature and high humidity environment is not clear, the compound derived from the non-transition metal M1 and the compound derived from the transition metal M2 are chemically bonded to each other in the region (a). It is presumed that a high-density region is formed by physical bonding by intermolecular interaction or the like. And it is estimated that a high-density area | region expresses high water vapor | steam barrier property, As a result, the water vapor | steam barrier property in the high temperature / humidity environment used as the acceleration test under high temperature / humidity environment time-lapse improves. Note that the above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention.

Hereinafter, each region constituting the gas barrier film will be described, but definitions of technical terms used will be described in advance.

In the specification of the present application, the “region” refers to a plane that is substantially perpendicular to the thickness direction of the gas barrier film (that is, a plane parallel to the outermost surface of the gas barrier film) and has a constant or arbitrary thickness. This refers to a three-dimensional range (region) between two opposing surfaces formed when divided by the thickness, and the composition of the constituent components in the region is gradually increased even if the composition in the thickness direction is constant. It may change.

As used herein, the “constituent component” refers to a compound constituting a specific region of a gas barrier film or a metal or non-metal simple substance. In addition, the “main component” in the present invention refers to a component having the maximum content as an atomic composition ratio. For example, “the main component of a metal element” refers to a metal element having the highest content ratio as an atomic composition ratio among the metal elements contained in the constituent components.

The gas barrier property of the gas barrier film according to one embodiment of the present invention is based on JIS K 7126-1987 when calculated with a laminate in which the gas barrier film is formed on a film formation target (for example, a substrate). The oxygen permeability measured by the method is preferably 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, preferably less than 1 × 10 ⁻⁵ ml / (m ² · 24 h · atm). More preferably, it is 1 × 10 ⁻⁶ ml / (m ² · 24 h · atm) or less (lower limit 0 ml / (m ² · 24 h · atm)). Further, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) is preferably a high water vapor barrier property of less than 1 × 10 ⁻⁵ g / (m ² · 24 h), more preferably less than 1 × 10 ⁻⁶ g / (m ² · 24 h). More preferably (lower limit 0 g / m ² · 24 h).

(Atomic composition profile)
The gas barrier film according to one embodiment of the present invention essentially contains a non-transition metal M1, a transition metal M2, and nitrogen. Note that the gas barrier film according to one embodiment of the present invention preferably includes only the non-transition metal M1 and the transition metal M2 as the metal element. The presence of non-transition metal M1, transition metal M2 and nitrogen in the gas barrier film can be confirmed by performing XPS (X-ray Photoelectron Spectroscopy) composition analysis of the gas barrier film as follows. .

(XPS analysis conditions)
The mixed region of the gas barrier film according to one embodiment of the present invention, the presence / absence of the region (a), the region (A) and the region (B), the composition distribution in these regions, the thickness of each region, and the like are as follows. It can be determined by measurement by X-ray photoelectron spectroscopy (abbreviation: XPS), which will be described in detail.

Hereinafter, a method for measuring each region by the XPS analysis method will be described.

The element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the gas barrier film according to one embodiment of the present invention is specifically a non-transition metal M1 (for example, silicon (Si)). The element concentration, element concentration of transition metal M2 (for example, niobium (Nb), tantalum (Ta), etc.), element concentration of oxygen (O), nitrogen (N), carbon (C), etc. It can be prepared by using the measurement and rare gas ion sputtering such as argon in combination, and sequentially performing surface composition analysis while exposing the inside from the surface of the gas barrier film.

The 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: atm%) and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time, the etching time is generally correlated with the distance in the thickness direction from the surface of the gas barrier film. The distance in the thickness direction from the surface of the gas barrier film calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement can be adopted as the “distance in the thickness direction”. 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 composition analysis of the gas barrier film according to one embodiment of the present invention will be shown.

・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profiles: in terms of SiO ₂ sputter thickness, repeat the measurement at a predetermined thickness intervals, - obtaining the depth depth profile Quantification relative sensitivity coefficients background determined by Shirley method, from the peak area obtained Quantify using the method. For data processing, MultiPak manufactured by ULVAC-PHI was used. The elements to be analyzed are non-transition metal M1 (for example, silicon (Si)), transition metal M2 (for example, niobium (Nb), tantalum (Ta), etc.), oxygen (O), nitrogen (N), carbon (C). In this measurement, other elements such as other metal elements may be analyzed as necessary.

The measurement resolution (predetermined thickness interval) of the depth profile may be 3 nm or less, 2 nm or less, or 1 nm or less. In the example described later, the measurement resolution of the depth profile is 1 nm.

Next, detailed explanation will be given for each area.

[Mixed area]
In the gas barrier film according to one embodiment of the present invention, in the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction, the value of the atomic ratio of the transition metal M2 to the non-transition metal M1 atom is 0. A mixed region, which is a region satisfying an elemental composition within a range of 0.02 to 49.

FIG. 1 is a schematic graph for explaining an element profile and a mixed region when a composition distribution of a non-transition metal M1 and a transition metal M2 is analyzed by an XPS method in a gas barrier film according to an embodiment of the present invention. It is. In addition, in this figure, although the gas barrier film | membrane which has the area | region (A) mentioned later and the area | region (B) is demonstrated, if a gas barrier film | membrane has a mixed area | region containing a area | region (a), it is. However, the present invention is not limited to this.

FIG. 1 shows the elemental analysis of non-transition metal M1, transition metal M2, oxygen (O), nitrogen (N), and carbon (C) in the depth direction from the surface of the gas barrier film (the left end of the graph). The horizontal axis represents the sputter depth (thickness: nm), and the vertical axis represents the content (atm%) of the non-transition metal M1 and the transition metal M2. Moreover, a dotted line shows the content rate of the non-transition metal M1, and a continuous line shows the content rate of the transition metal M2. From the right side of the graph, a region (A) region having an elemental composition mainly composed of a non-transition metal M1 (for example, silicon (Si)) as a metal is shown, and a transition metal as a metal is in contact with the region on the left side of the graph. A region (B) having an elemental composition mainly composed of M2 (for example, niobium (Nb), tantalum (Ta), etc.) is shown. It is shown that the gas barrier film has a mixed region. As shown in this figure, when the gas barrier film has a region (A) and a region (B) to be described later, the mixed region includes a part of the region (A) and a part of the region (B). It becomes the area shown overlapping.

A preferable type of non-transition metal M1 in the mixed region is the same as a preferable type of non-transition metal M1 in the region (A) described later, and a preferable type of transition metal M2 in the mixed region is preferable in region (B) described later. This is the same as the type of transition metal M2.

The thickness of the mixed region is not particularly limited, but it is preferably 5 nm or more continuously in the thickness direction. The reason is that the presence of 5 nm or more continuously in the thickness direction increases the flexibility improvement effect, and the region (a) described later is more easily formed. From the same viewpoint, the thickness of the mixed region is preferably 8 nm or more continuously in the thickness direction, more preferably 10 nm or more, and further preferably 20 nm or more. The thickness of the mixed region is not particularly limited, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics.

Here, since the mixed region may have a nitrogen atom, the composition thereof can be expressed as M1M2 _x N _y (0.02 ≦ x ≦ 49, y ≧ 0).

The mixed region includes a compound derived from non-transition metal M1 (non-transition metal M1 simple substance or a compound containing non-transition metal M1 simple substance) and a compound derived from transition metal M2 (a compound containing transition metal M2 simple substance or transition metal M2). And a compound derived from the non-transition metal M1 and the transition metal M2 may be included as a constituent component. Moreover, both of these may be included as constituent components.

Here, in this specification, the mixture of the compound derived from the non-transition metal M1 and the compound derived from the transition metal M2 in the mixed region is derived from the compound derived from the non-transition metal M1 and the transition metal M2. A compound in a state where it is mixed with each other without chemically bonding to each other. Examples of the mixture include those in a state where niobium oxide and silicon oxide are mixed without being chemically bonded to each other.

When a mixture of a compound derived from the non-transition metal M1 and a compound derived from the transition metal M2 is included in the mixed region, a preferable compound derived from the non-transition metal M1 in the mixture is the region (A) described later. The same as the compound derived from the preferred non-transition metal M1. Moreover, the compound derived from the preferable transition metal M2 in the said mixture is the same as the compound derived from the preferable transition metal M2 in the area | region (A) mentioned later.

In this specification, the compound derived from the non-transition metal M1 and the transition metal M2 is a compound in which the compound derived from the non-transition metal M1 and the compound derived from the transition metal M2 are chemically bonded to each other. It represents a formed compound or a compound formed by physical bonding by intermolecular interaction or the like. In the present specification, the compound derived from the non-transition metal M1 and the transition metal M2 has, for example, a structure in which a niobium atom and a silicon atom form a chemical bond directly or through an oxygen atom. Compounds and the like.

In the mixed region, the composition generally changes continuously or stepwise in the thickness direction of the gas barrier film. Therefore, the mixed region can suppress stress concentration, and an excellent flexibility of the gas barrier film is realized. From the viewpoint of flexibility, the composition of the mixed region preferably changes continuously.

In the gas barrier film according to the present invention, since the mixed region includes a region (a) described later, the maximum value of the existing atomic ratio of nitrogen atoms to non-transition metal M1 atoms in the mixed region is 0. It will be shown with an elemental composition greater than .6. It is preferable that the position of the mixed region having the maximum value is included in the region (a) described later.

The mixed region is preferably formed in the vicinity of the interface between the region (A) and the region (B) of the gas barrier film. At this time, the flexibility improving effect of the gas barrier film due to the composition changing continuously or stepwise is further increased. That is, the gas barrier film according to a preferred embodiment of the present invention includes a region (A) containing the non-transition metal M1 as the main component of the metal element and a transition metal M2 as the main component of the metal element in the thickness direction. Region (B), and the region (A) and the region (B) are in contact with each other.

[Area (a)]
The region (a) represents a region where M1M2 _x N _y has a specific composition in the above-described mixed region. The gas barrier film of the present invention having such a configuration can achieve both excellent flexibility and high water vapor barrier property in a high temperature and high humidity environment. The gas barrier film according to one embodiment of the present invention has the following formula (1) when the composition is represented by M1M2 _x N _y in an atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction. It has the area | region (a) (henceforth only area | region (a)) which satisfies following formula (2).

x is the existing atomic ratio of the transition metal M2 to the non-transition metal M1, and y is the existing atomic ratio of nitrogen to the non-transition metal M1, but the region (a) represents the formula (1) and the formula (2). It is necessary to be satisfied at the same time. That is, at least the region where the non-transition metal M1 atom and the transition metal M2 atom are present at the same time, and the existing atomic ratio of the transition metal M2 to the non-transition metal M1 atom (transition metal M2 atom / non-transition metal M1 atom) It has been found that 0.2 or more and 3.0 or less is a condition for developing a high water vapor barrier property in a high temperature and high humidity environment. Here, even if the atomic ratio of transition metal M2 to non-transition metal M1 atom (transition metal M2 atom / non-transition metal M1 atom) is less than 0.2 or more than 3.0, no transition Since the bond between the metal M1 atom and the transition metal M2 atom is reduced, it is considered that the water vapor barrier property in a high temperature and high humidity environment is lowered. Then, a region in which a non-transition metal M1 atom, a transition metal M2 atom, and a nitrogen atom exist at the same time is formed, and an existing atomic ratio of the transition metal M2 to the non-transition metal M1 atom (transition metal M2 atom / non-transition metal M1 atom) Is 0.2 or more and 3.0 or less, and the atomic ratio of the nitrogen atom to the non-transition metal M1 atom (nitrogen atom / non-transition metal M1 atom) is more than 0.6 and 1.4 or less, This is a condition for developing an extremely high water vapor barrier property in a high temperature and high humidity environment.

Since the region (a) can impart a high water vapor barrier property in a high temperature and high humidity environment to the gas barrier film, the gas barrier film has a water vapor barrier in a high temperature and high humidity environment at a level required for an organic EL element or the like. The film can be made thin while maintaining the flexibility, and has excellent flexibility.

When the region (a) has a plurality of kinds of non-transition metals M1 or a plurality of kinds of transition metals M2, x is calculated from the sum of weights of the contents of the respective metals.

The embodiment using silicon as the non-transition metal M1 is particularly preferable because the water vapor barrier property in a high temperature and high humidity environment can be remarkably improved.

Here, in the region (a), the maximum value (y maximum value) of the nitrogen atom existing atom ratio with respect to the non-transition metal M1 atom is indicated by the element composition within the range of y, and therefore, more than 0.6. Although it is 4 or less, it is preferably 0.65 or more from the viewpoint of obtaining a higher water vapor barrier property in a high temperature and high humidity environment. In addition, the maximum value of the atomic ratio of nitrogen atoms to the non-transition metal M1 atom (y maximum value) is preferably 1 or less from the viewpoint of obtaining a higher water vapor barrier property in a high temperature and high humidity environment, More preferably, it is 0.9 or less.

The region (a) is a region that satisfies the above formula (1) and the above formula (2) when the composition is represented by M1M2 _x N _y . Here, from the viewpoint of further improving the water vapor barrier property in a high-temperature and high-humidity environment, the region (a) is preferably present in a thickness direction of 1 nm or more, more preferably 2 nm or more, More preferably, it is 3 nm or more, and particularly preferably 4 nm or more. Then, when both the non-transition metal M1 containing layer and the transition metal M2 containing layer, which will be described later, are formed by vapor phase film formation, extremely high flexibility and extremely high water vapor barrier properties in a high temperature and high humidity environment are obtained. From the viewpoint of obtaining stably, the region (a) is most preferably 5 nm or more continuously in the thickness direction. Thus, a preferred embodiment of the present invention is a gas barrier film according to an embodiment of the present invention, wherein the thickness of the region (a) is 5 nm or more. Further, the region (a) is not particularly limited, but from the viewpoint of obtaining a better light transmittance, it is preferably continuously present in the thickness direction of 30 nm or less, more preferably 15 nm or less, More preferably, it is 10 nm or less, and particularly preferably 8 nm or less.

The composition and thickness of such a region (a) are controlled by a method for forming a non-transition metal M1-containing layer and a transition metal M2-containing layer, a forming order, and a non-transition metal M1-containing in a gas barrier film manufacturing method described later. After forming a layer (or transition metal M2 containing layer), it can carry out by selecting suitably the storage method etc. until forming a transition metal M2 containing layer (or non-transition metal M1 containing layer).

[Area (A)]
The gas barrier film according to one embodiment of the present invention includes a region (A) containing a non-transition metal M1 as a main component of a metal element (also simply referred to as “region (A)” in this specification). preferable.

The existence of a region containing the non-transition metal M1 as a main component of the metal element in the thickness direction of the gas barrier film can be confirmed by composition analysis by the XPS analysis method described above.

In the thickness direction of the gas barrier film, the metal element having the maximum atomic composition ratio is the non-transition metal M1 and the transition metal M2, that is, the atomic composition of the non-transition metal M1 in the metal element. The ratio and the atomic composition ratio of the transition metal M2 may both be maximum and the same. In the present invention, such a region (or point) is assumed to be included in the region (A).

Here, from the viewpoint of further improving the water vapor barrier property in a high temperature and high humidity environment, the non-transition metal M1, the transition metal M2, oxygen (O), nitrogen (N) and carbon (C) in the region (A). The average value in the thickness direction of the ratio of the amount of non-transition metal M1 atoms to the total amount of atoms (unit: atm%) (hereinafter also referred to as [M1]) is preferably 20 atm% or more, and 22 atm % Or more, more preferably 24 atm% or more. Further, from the viewpoint of obtaining better light transmittance, the average value in the thickness direction of [M1] in the region (A) is preferably 40 atm% or less, and more preferably 38 atm% or less. Preferably, it is 36 atm% or less.

As described above, the ratio of the amount of non-transition metal M2 atoms to the total amount of [M1] and non-transition metal M1, transition metal M2, oxygen (O), nitrogen (N), and carbon (C) atoms. When there is a region (or point) where (unit: atm%) (hereinafter also referred to as [M2]) has the same value, from the viewpoint that the water vapor barrier property in a high-temperature and high-humidity environment is further increased, The same value is preferably 10 atm% or more and 25 atm% or less, and more preferably 12 atm% or more and 20 atm% or less.

The region (A) may contain atoms other than the non-transition metal M1, the transition metal M2, oxygen (O), nitrogen (N), and carbon (C), for example, hydrogen. Here, the atomic weight ratio (unit: atm%) of the hydrogen in the region (A) can be measured by Rutherford Backscattering Spectroscopy (RBS) or HFS analysis (Hydrogen Forwarding Scattering Spectrometry). However, from the viewpoint that the water vapor barrier property in a high-temperature and high-humidity environment is further increased, the non-transition metal M1, transition metal M2, oxygen (O), nitrogen (to the total amount of all atoms present in the region (A) ( The average value in the thickness direction of the ratio of the total amount of N) and carbon (C) atoms (unit: atm%) is preferably 90 atm% or more, more preferably 95 atm% or more, and 99 atm. % Or more is more preferable (upper limit of 100 atm%).

The non-transition metal M1 is not particularly limited, but is a metal selected from the non-transition metal M1 selected from the metals of Groups 12 to 14 of the long-period periodic table from the viewpoint of water vapor barrier properties. Is preferred. Among these, it is more preferable that Si, Al, Zn, In, or Sn is included, it is more preferable that Si, Sn, or Zn is included, and it is particularly preferable that Si is included. Thus, a preferred embodiment of the present invention is a gas barrier film in which the non-transition metal M1 is Si. The non-transition metal M1 may be used alone or in combination of two or more.

The form of the non-transition metal M1 as a constituent component of the region (A) is not particularly limited as long as it is a compound derived from the non-transition metal M1 (non-transition metal M1 alone or a compound containing the non-transition metal M1). For example, the non-transition metal M1 is included in the state of an oxide, nitride, carbide, oxynitride, or oxycarbide of the non-transition metal M1. Especially, it is preferable that the non-transition metal M1 is contained in the state of the compound containing the non-transition metal M1, and it is more preferable that it is contained in the state of the compound containing the non-transition metal M1 and nitrogen. In addition, the form of the non-transition metal M1 included in the region (A) may be a single type or a combination of two or more types.

The region (A) may be a single layer or a laminated structure of two or more layers. When area | region (A) is a laminated structure of two or more layers, the non-transition metal compound contained in area | region (A) may be the same, and may differ.

The thickness of the region (A) (the total thickness in the case of a laminated structure of two or more layers) is preferably 5 nm or more, more preferably 10 nm or more from the viewpoint of water vapor barrier properties. In addition, the thickness of the region (A) is not particularly limited, but may be 100 nm or less, 50 nm or less, or 30 nm or less from the presumed mechanism by which the region (A) is formed. Good.

[Area (B)]
The gas barrier film according to one embodiment of the present invention preferably includes a region (B) containing a transition metal M2 as a main component of a metal element (also simply referred to as “region (B)” in this specification). .

The presence of a region containing the transition metal M2 as a main component of the metal element in the thickness direction of the gas barrier film can be confirmed by composition analysis using the XPS analysis method described above.

Here, from the viewpoint that the water vapor barrier property in a high temperature and high humidity environment is further increased, the average value in the thickness direction of [M2] in the region (B) is preferably 16 atm% or more, and 18 atm%. More preferably, it is more preferably 20 atm% or more. Further, from the viewpoint of obtaining better light transmittance, the average value in the thickness direction of [M2] in the region (B) is preferably 40 atm% or less, more preferably 38 atm% or less. Preferably, it is 36 atm% or less.

Note that the region (B) may contain atoms other than the non-transition metal M1, the transition metal M2, oxygen (O), nitrogen (N), and carbon (C), for example, hydrogen. Here, the method for measuring the ratio of atomic weight of hydrogen in the region (B) (unit: atm%) is the same as the ratio of atomic weight of hydrogen in the region (A). However, from the viewpoint that the water vapor barrier property in a high-temperature and high-humidity environment is further increased, the non-transition metal M1, transition metal M2, oxygen (O), nitrogen (with respect to the total amount of all atoms present in the region (B) ( The average value in the thickness direction of the ratio of the total amount of N) and carbon (C) atoms (unit: atm%) is preferably 90 atm% or more, more preferably 95 atm% or more, and 99 atm%. More preferably, the upper limit is 100 atm%.

The transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y , Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W , Re, Os, Ir, Pt, and Au.

Among these, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like can be cited as transition metals (M2) that can provide good water vapor barrier properties. Among these, Nb, Ta, and V, which are Group 5 elements, are particularly preferably used from the viewpoint of easy bonding to the non-transition metal (M1) contained in the gas barrier film from various examination results. it can. Thus, in the gas barrier film according to a preferred embodiment of the present invention, the transition metal M2 is at least one metal selected from the group consisting of Nb, Ta, and V.

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

The form of the transition metal M2 as a constituent component of the region (B) is not particularly limited as long as it is a compound derived from the transition metal M2 (a compound containing the transition metal M2 alone or the transition metal M2). For example, the transition metal M2 is included in the state of an oxide, nitride, carbide, oxynitride, or oxycarbide of the transition metal M2. Especially, it is preferable that the transition metal M2 is contained in the state of the compound containing the transition metal M2, and it is more preferable that it is contained in the state of the transition metal oxide. The transition metal M2 included in the region (B) may be used alone or in combination of two or more.

The region (B) may be a single layer or a laminated structure of two or more layers. When the region (B) has a laminated structure of two or more layers, the transition metal M2 compound contained in the region (B) may be the same or different.

The region (B) is formed adjacent to the region (A), thereby forming the region (a) and imparting high water vapor barrier property in a high temperature and high humidity environment. The water vapor barrier property is not necessarily required for (B) itself. Accordingly, the region (B) can be effective even with a relatively thin layer. Specifically, from the viewpoint of forming the region (a) with a thickness that realizes higher water vapor barrier properties in a high-temperature and high-humidity environment, the thickness of the region (B) is preferably 2 nm or more, It is more preferably 4 nm or more, further preferably 5 nm or more, and particularly preferably 6 nm or more. In addition, the thickness of the region (B) is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 25 nm or less, from the viewpoint of obtaining better light transmittance. 15 nm or less is particularly preferable, and 12 nm or less is extremely preferable.

[Stacking order of region (A) and region (B)]
In the gas barrier film according to one embodiment of the present invention, the stacking order of the region (A) and the region (B) is not particularly limited, and the film is formed on a film formation target (for example, a resin base material). It may be arranged in the order of region (A) / region (B) from the object side, or arranged in the order of region (B) / region (A) on the film formation object from the film formation object side. May be. However, the arrangement of the region (A) / region (B) in this order on the film formation object from the film formation object side results in higher water vapor barrier properties and superior flexibility in a high temperature and high humidity environment. From the viewpoint of obtaining Further, within the range of the thickness of the gas barrier film capable of obtaining excellent flexibility, the gas barrier film is a unit having a layered structure of region (A) / region (B) or region (B) / region (A). You may have the structure where the unit which consists of these laminated structures laminated | stacked two or more, for example, an alternating laminated structure.

<Method for producing gas barrier film>
Although the manufacturing method of the gas barrier film | membrane which concerns on one form of this invention is not restrict | limited in particular, It is preferable to include forming a non-transition metal M1 content layer and a transition metal M2 content layer so that both may touch.

That is, the second embodiment of the present invention includes a non-transition metal M1 containing layer containing the non-transition metal M1 as a main component of the metal element, and a transition metal M2 containing layer containing the transition metal M2 as the main component of the metal element. A method for producing a gas barrier film, comprising:
In the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction of the gas barrier film, the following formula (1) and the following formula (2) are satisfied when the composition is represented by M1M2 _x N _y A method for manufacturing a gas barrier film having a region (a) to be processed.

According to the second embodiment of the present invention, it is also possible to provide means capable of achieving both excellent flexibility and high water vapor barrier property in a high temperature and high humidity environment in the gas barrier film. Moreover, according to the manufacturing method of the gas barrier film which concerns on the 2nd form of this invention, the gas barrier film which concerns on the 1st form of this invention demonstrated above can be manufactured.

FIG. 2 is a schematic cross-sectional view showing a laminated structure formed in the method for producing a gas barrier film according to one embodiment of the present invention, and FIG. 3 shows a gas barrier film according to another embodiment of the present invention. It is a cross-sectional schematic diagram which shows the laminated structure formed in a manufacturing method. Here, in the laminated structure 10 of the gas barrier film formed on the film formation target according to FIG. 2, the non-transition metal M1 containing layer 12 is formed on the film formation target 11 and then the transition metal M2 containing layer 13 is formed. Is formed. Further, in the laminated structure 10 ′ of the gas barrier film formed on the film formation target according to FIG. 3, the transition metal M2 containing layer 13 is formed on the film formation target 11, and then the non-transition metal M1 containing layer 12 is formed. Is formed. 2 and 3, the non-transition metal M1 containing layer 12 and the transition metal M2 containing layer 13 are formed so that they are in contact with each other. The film formation target 11 is not particularly limited as long as it is a target on which a gas barrier film can be formed. For example, when a gas barrier film is manufactured, the film formation target 11 can be a resin base material on which layers having various functions are formed as necessary. The mixed region including the region (A), the region (B), and the region (a) is obtained after the formation of the non-transition metal M1 containing layer 12 (or the transition metal M2 containing layer 13) and the transition metal M2 containing layer 13 (or non As a result of the formation of the transition metal M1 containing layer 12), the substance containing the transition metal M2 enters the non-transition metal M1 containing layer 12 or the substance containing the non-transition metal M1 enters the transition metal M2 containing layer 13. It is thought that it is formed. Further, in the mixed region including the region (A), the region (B), and the region (a), after the non-transition metal M1 containing layer and the transition metal M2 containing layer are formed, spontaneous diffusion of the substance occurs between these layers. It is thought that it is formed as a result.

Here, the composition and thickness of the region (a) are controlled by the formation method, formation order of the non-transition metal M1-containing layer and the transition metal M2-containing layer, and the non-transition metal M1-containing layer (or the transition metal M2-containing layer). After forming, it can be performed by a storage method or the like until a transition metal M2 containing layer (or a non-transition metal M1 containing layer) is formed.

In the method for producing a gas barrier film according to one embodiment of the present invention, the order of formation of the non-transition metal M1 containing layer and the transition metal M2 containing layer is not particularly limited, and a film formation target (for example, a resin base material or the like) ), A non-transition metal M1 containing layer / a transition metal M2 containing layer may be formed in this order from the film forming object side, or the transition metal M2 containing may be formed on the film forming object from the film forming object side. You may form in order of a layer / non-transition metal M1 content layer. However, the formation of the non-transition metal M1 containing layer / transition metal M2 containing layer in this order on the film forming object from the film forming object side has a higher water vapor barrier property in a high temperature and high humidity environment and more excellent It is preferable from the viewpoint of obtaining flexibility. This is because formation of the region (a) is easier and the thickness of the region (a) can be further increased. In addition, within the thickness range of the gas barrier film that provides excellent flexibility, the method for producing the gas barrier film includes a unit comprising a non-transition metal M1 containing layer / transition metal M2 containing layer or a transition metal M2 containing layer / A method of repeatedly forming units composed of the non-transition metal M1-containing layer to form a laminated structure, for example, an alternating laminated structure may be used.

Note that the gas barrier film manufactured by the method for manufacturing a gas barrier film according to one embodiment of the present invention is the same as the above-described gas barrier film according to one embodiment of the present invention.

[Formation of non-transition metal M1-containing layer]
The method for forming the non-transition metal M1-containing layer is not particularly limited, and examples thereof include a vapor deposition method and a coating method. Among these, from the viewpoint that the non-transition metal M1-containing layer and the transition metal M2-containing layer can be continuously formed while conveying the film formation target, and it is excellent in productivity, this is a vapor phase film formation method. It is preferable. Here, as a method of forming each layer while conveying the film formation target, for example, a roll-to-roll method may be mentioned. That is, the manufacturing method according to a preferred embodiment of the present invention is a manufacturing method including forming the non-transition metal M1-containing layer by a vapor deposition method.

In one embodiment of the present invention, the raw material for forming the non-transition metal M1-containing layer is particularly limited as long as it is a compound derived from the non-transition metal M1 (non-transition metal M1 alone or a compound containing the non-transition metal M1). Not. Moreover, as a raw material for forming a non-transition metal M1 content layer, the substance (a metal simple substance, the compound containing a metal) derived from another metal may further be contained. In this case, the raw material of the non-transition metal M1 containing layer further includes a raw material capable of forming the transition metal M2 containing layer, that is, a substance derived from the transition metal M2 (transition metal M2 alone, a compound containing the transition metal M2). It may be. In this case, the layer classification is determined as follows. First, only the non-transition metal M1-containing layer is separately formed on the film formation target under the same conditions as the production of the gas barrier film. Next, the atomic composition ratio (atm%) of the metal element contained in the constituent components and the atomic composition ratio (atm%) of the non-transition metal M1 are measured in the XPS analysis method in the same manner as the atomic composition profile of the gas barrier film described above. To measure. And among the metal elements contained in the constituent components in the produced layer, the layer having the maximum content of the non-transition metal M1 as the atomic composition ratio is treated as the formation of the non-transition metal M1-containing layer.

(Vapor deposition method)
The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, chemical vapor deposition (CVD), and ALD. Examples thereof include chemical vapor deposition methods such as (Atomic Layer Deposition). Among these, the physical vapor deposition method is preferable, the sputtering method or the CVD method is more preferable, and the sputtering method is more preferable because the film formation is possible without damaging the object to be formed and the productivity is high.

The film formation set thickness when forming a layer containing the non-transition metal M1 by the vapor deposition method (the total thickness in the case of a laminated structure of two or more layers) is 10 nm or more from the viewpoint of water vapor barrier properties. It is preferable that the thickness is 30 nm or more. In addition, the film formation setting thickness when the layer containing the non-transition metal M1 is formed by the vapor phase film formation method is preferably 500 nm or less, and more preferably 300 nm or less from the viewpoint of flexibility.

The non-transition metal M1 containing layer is calculated from the result of the atomic composition distribution profile obtained when XPS composition analysis is performed, and the thickness direction of the existing atomic ratio of nitrogen atoms to non-transition metal M1 atoms (N / M1) Is preferably 0.10 or more, particularly preferably 0.50 or more, and very preferably 0.90 or more. When the average value in the thickness direction of the existing atomic ratio (N / M1) of nitrogen atoms to non-transition metal M1 atoms is 0.90 or more, the region (a) is more easily formed in the mixed region. Further, in the formation of the transition metal M2 containing layer, the transition metal M2 containing layer is made to be nitrogen by, for example, using a transition metal M2 nitride or oxynitride as a raw material and introducing nitrogen during film formation. When forming as a layer containing, the region (a) is more easily formed in the mixed region. At this time, when forming a layer containing nitrogen as the transition metal M2 containing layer, the average value in the thickness direction of the existing atomic ratio of nitrogen atoms to non-transition metal M1 atoms (N / M1) is 0.50 or more. Preferably there is. This is because the region (a) can be formed more favorably within the above range. From the same viewpoint, when forming a layer containing nitrogen as the transition metal M2 containing layer, the average value in the thickness direction of the existing atomic ratio of nitrogen atoms to non-transition metal M1 atoms (N / M1) is 0. It is more preferably 60 or more, further preferably 0.80 or more, particularly preferably 0.85 or more, and extremely preferably 0.90 or more. Moreover, it is preferable that the average value of the thickness direction of the atomic ratio (N / M1) of the nitrogen atom with respect to the non-transition metal M1 atom is 1.4 or less. The XPS measurement analysis and the atomic composition distribution profile used here are the same as those described in the description of the atomic composition profile.

When the non-transition metal M1 containing layer is formed by the vapor deposition method, for example, the ratio of the non-transition metal M1 and oxygen in the film forming raw material, the ratio of the inert gas and the reactive gas at the time of film formation, By adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation, The composition and thickness of region (a) can be controlled.

≪CVD≫
The chemical vapor deposition (CVD) method is a raw material gas containing a target thin film component on a material for forming a non-transition metal M1-containing layer of a film formation target (for example, a resin base material). And a film is deposited by a chemical reaction in the surface or gas phase of the material forming the non-transition metal M1 containing layer. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. Law. These methods are not particularly limited, but it is preferable to apply the plasma CVD method from the viewpoint of the film forming speed and the processing area. Forming the non-transition metal M1 containing layer by chemical vapor deposition is advantageous in terms of water vapor barrier properties in a high temperature and high humidity environment. Further, when a layer containing a non-transition metal M1 is formed by a vacuum plasma CVD method or a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, a metal compound, a decomposition gas, a decomposition temperature, which is a raw material (also referred to as a raw material), By selecting conditions such as input power, a non-transition metal M1-containing layer having a target composition can be formed, which is preferable.

Here, as the plasma CVD, CCP (Capacitively Coupled Plasma Capacitively Coupled Plasma) -CVD, ICP (Inductively Coupled Plasma Inductively Coupled Plasma) -CVD, microwave CVD, ECR (Electron Cyclotron Resonance CVD, Large CVD) Various plasma CVD methods such as the above are preferably used.

The apparatus used for the plasma CVD method is not particularly limited, and a known apparatus can be used. For example, a commercially available vacuum CCP (Capacitively Coupled Plasma Capacitively Coupled Plasma) -CVD apparatus may be used.

The source gas used in the plasma CVD method is not particularly limited. When the non-transition metal M1 is silicon, silane gas, disilane gas, TEOS (tetraethoxysilane), HMDSO (hexamethyldisiloxane), HMDSN (hexamethyldi). Source gases used in the deposition of silicon-containing films by known plasma CVD methods such as silazane), TMS (tetramethylsilane), hydrazine gas, ammonia gas, nitrogen gas, hydrogen gas, argon gas, neon gas, helium gas May be appropriately selected and used. A preferable example of the source gas includes a combination of silane gas, ammonia gas, and hydrogen gas. Here, from the viewpoint of further improving the water vapor barrier property in a high-temperature and high-humidity environment, the raw material gas preferably contains nitrogen gas. A more preferable example of the source gas includes a combination of silane gas, ammonia gas, hydrogen gas and nitrogen gas.

Here, the flow rate of the source gas is preferably 10 to 1000 sccm, more preferably 100 to 800 sccm, and further preferably 200 to 700 sccm. The ratio of the nitrogen gas flow rate to the raw material gas flow rate is preferably 0 to 70%, more preferably 30 to 60%.

Also, the film formation conditions may be set appropriately according to the source gas used, the thickness of the layer to be formed, and the like. At the time of film formation, the supply amount of the reaction gas, the supply balance of each reaction gas, the film formation pressure, the plasma excitation power, the plasma excitation frequency, the power applied such as the bias, the temperature of the film formation target (for example, the substrate), the film formation By appropriately controlling the front pressure, the distance between the film formation target and the plasma generation region, and the like, the non-transition metal M1 containing layer can be controlled, and the composition of the gas barrier film can be controlled. For example, the distance between the electrodes is preferably 10 to 40 mm. For example, the film forming pressure in the chamber is preferably 1 to 100 Pa. For example, the plasma excitation power is preferably 100 to 2000 W.

Hereinafter, with reference to FIG. 4, the vacuum plasma CVD method, which is a preferred form among the CVD methods, will be described in detail. FIG. 4 is a schematic diagram showing an example of a vacuum plasma CVD apparatus that can be used to form the non-transition metal M1-containing layer.

4, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided.

The heating / cooling device 160 is configured to measure the temperature of the heat medium, heat or cool the heat medium to a stored set temperature, and supply the heat medium to the susceptor 105. The supplied heat medium flows inside the susceptor 105, heats or cools the susceptor 105, and returns to the heating / cooling device 160. At this time, the temperature of the heat medium is higher or lower than the set temperature, and the heating and cooling device 160 heats or cools the heat medium to the set temperature and supplies the heat medium to the susceptor 105. In this manner, the cooling medium circulates between the susceptor and the heating / cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium having the set temperature.

The vacuum chamber 102 is connected to an evacuation system 107, and before the film formation process is started by the vacuum plasma CVD apparatus 101, the inside of the vacuum chamber 102 is evacuated in advance and the heat medium is heated from room temperature. The temperature is raised to a set temperature, and a heat medium having the set temperature is supplied to the susceptor 105. The susceptor 105 is at room temperature at the start of use, and when a heat medium having a set temperature is supplied, the susceptor 105 is heated.

After circulating the heat medium at a set temperature for a certain period of time, the film formation object (for example, a resin substrate or the like) 110 is carried into the vacuum chamber 102 while maintaining the vacuum atmosphere in the vacuum chamber 102 and placed on the susceptor 105. Deploy.

A large number of nozzles (holes) are formed on the surface of the cathode electrode 103 facing the susceptor 105. The cathode electrode 103 is connected to a gas introduction system 108. When a CVD gas is introduced from the gas introduction system 108 to the cathode electrode 103, the CVD gas is ejected from the nozzle of the cathode electrode 103 into the vacuum chamber 102 in a vacuum atmosphere. The cathode electrode 103 is connected to a high frequency power source 109, and the susceptor 105 and the vacuum chamber 102 are connected to the ground potential.

When a CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102, a high-frequency power source 109 is activated while supplying a heat medium having a constant temperature from the heating / cooling device 160 to the susceptor 105, and a high-frequency voltage is applied to the cathode electrode 103, Plasma of the introduced CVD gas is formed. When the CVD gas activated in the plasma reaches the surface of the film formation target 110 on the susceptor 105, a thin film that is a non-transition metal M1-containing layer grows on the surface of the film formation target 110. At this time, the distance between the susceptor 105 and the cathode electrode 103 is set as appropriate.

Further, the flow rates of the raw material gas and the cracked gas are appropriately set in consideration of the raw material gas, the cracked gas type, and the like. In one embodiment, the flow rate of the source gas is 30 to 300 sccm, and the flow rate of the decomposition gas is 100 to 1000 sccm.

During the growth of the thin film, a heating medium having a constant temperature is supplied from the heating / cooling device 160 to the susceptor 105, and the susceptor 105 is heated or cooled by the heating medium, and a thin film is formed while being maintained at a constant temperature. Generally, the lower limit temperature of the growth temperature when forming a thin film is determined by the film quality of the thin film, and the upper limit temperature is determined by the allowable range of damage to the thin film already formed on the film formation target 110. The lower limit temperature and the upper limit temperature vary depending on the material of the thin film to be formed, the material of the already formed thin film, etc., but the preferable lower temperature for ensuring the film quality with a high water vapor barrier property is 50 ° C. or higher, and the upper limit temperature is It is preferable that it is below the heat-resistant temperature of the film-forming target.

The correlation between the film quality of the thin film formed by the vacuum plasma CVD method and the deposition temperature, and the correlation between the damage to the deposition object 110 and the deposition temperature are obtained in advance, and the lower limit temperature and the upper limit temperature are determined. . For example, the temperature of the film formation target 110 during the vacuum plasma CVD process is preferably 50 to 250 ° C.

Furthermore, the relationship between the temperature of the heating medium supplied to the susceptor 105 and the temperature of the film formation object 110 when plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 103 is measured in advance. In order to maintain the temperature of the film formation target 110 at a value between the lower limit temperature and the upper limit temperature during the vacuum plasma CVD process, the temperature of the heat medium supplied to the susceptor 105 is required. For example, a lower limit temperature (preferably 50 ° C.) is stored, and a heat medium whose temperature is controlled to a temperature equal to or higher than the lower limit temperature is set to be supplied to the susceptor 105. The heat medium refluxed from the susceptor 105 is heated or cooled, and a heat medium having a set temperature (preferably 50 ° C. or higher) is supplied to the susceptor 105. Here, for example, by supplying a mixed gas of silane gas, ammonia gas, and nitrogen gas as a CVD gas, and maintaining the film formation object 110 at a temperature condition not lower than the lower limit temperature but not higher than the upper limit temperature, the nitridation that is a silicon-containing layer A silicon (SiN) film is formed.

Immediately after the startup of the vacuum plasma CVD apparatus 101, the susceptor 105 is at room temperature, and the temperature of the heat medium returned from the susceptor 105 to the heating / cooling apparatus 160 is lower than the set temperature. Therefore, immediately after the activation, the heating / cooling device 160 heats the refluxed heat medium to raise the temperature to the set temperature, and supplies it to the susceptor 105. In this case, the susceptor 105 and the film formation target 110 are heated and heated by the heat medium, and the film formation target 110 is maintained in the range of the lower limit temperature or more and the upper limit temperature or less.

When a thin film is continuously formed on a plurality of deposition objects 110, the susceptor 105 is heated by heat flowing from the plasma. In this case, since the heat medium recirculated from the susceptor 105 to the heating / cooling device 160 is higher than the lower limit temperature (preferably 50 ° C.), the heating / cooling device 160 cools the heat medium, and the heat medium having a set temperature. Is supplied to the susceptor 105. Thereby, it is possible to form a thin film while maintaining the film formation target 110 in the range of the lower limit temperature or higher and the upper limit temperature or lower. Thus, the heating / cooling device 160 heats the heating medium when the temperature of the refluxed heating medium is lower than the set temperature, and cools the heating medium when the temperature is higher than the set temperature. In addition, a heat medium having a set temperature is supplied to the susceptor, and as a result, the film formation target 110 is maintained in a temperature range between the lower limit temperature and the upper limit temperature. When the thin film is formed to a predetermined film thickness, the film formation target 110 is carried out of the vacuum chamber 102, and the non-film formation target 110 is carried into the vacuum chamber 102. A thin film is formed while supplying a heat medium.

≪Spatter≫
Film formation by sputtering is advantageous in that the film formation rate is higher and the productivity is higher. Further, it is extremely high to form both the non-transition metal M1 containing layer and the transition metal M2 containing layer by the sputtering method, and in particular, to form each layer continuously by the sputtering method while conveying the film formation target. There is an advantage of having productivity.

For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. In addition, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. The reactive sputtering method is preferable because the metal oxide film can be formed at a high film formation speed by controlling the sputtering phenomenon so as to be in the transition region. When performing DC sputtering or DMS sputtering, a thin film of an oxide of non-transition metal M1 is formed by using a target containing non-transition metal M1 as a target and introducing oxygen into the process gas. Can do. In the case of forming a film by RF sputtering, an oxide target of the non-transition metal M1 can be used. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a thin film such as an oxide, nitride, nitride oxide, or carbonate of the non-transition metal M1 can be formed. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like. For example, the film forming pressure is preferably 0.1 to 5 Pa. Further, for example, the sputtering power source power is preferably 2 to 10 W / cm ² .

The kind of non-transition metal M1 included in the target and the preferred kind of non-transition metal M1 are the same as those of the non-transition metal M1 described for the region (A). Further, as the target including the non-transition metal M1, the same compound as the compound derived from the non-transition metal M1 described for the region (A) can be used. Here, as a particularly preferable example of the target including the non-transition metal M1, a commercially available silicon target can be given. Examples of the target containing the non-transition metal M1 are described in, for example, JP 2000-026961 A, JP 2009-215651 A, JP 2003-160862 A, and JP 2012-007218 A. A target containing a plurality of elements can be used.

(Coating method)
The non-transition metal M1 containing layer may be formed by a coating method. A non-transition metal M1 content layer can be obtained by apply | coating and drying the coating liquid containing the compound containing non-transition metal M1. The layer containing the non-transition metal M1 formed by the coating method is a layer having few defects because there is no contamination of foreign substances such as particles during film formation. The non-transition metal M1 containing layer may be a single layer or a laminated structure of two or more layers.

The non-transition metal M1 containing layer formed by the coating method has an atomic ratio (N / N) of nitrogen atoms to non-transition metal M1 atoms calculated from the result of the atomic composition distribution profile obtained when XPS composition analysis is performed. The maximum value in the thickness direction in a region within 30 nm from the surface layer side (the surface side in contact with the transition metal M2 containing layer) of the non-transition metal M1 containing layer of M1) is preferably 0.50 or more. It is very preferable that it is 90 or more. When the maximum value in the thickness direction of the atomic ratio (N / M1) of nitrogen atoms to non-transition metal M1 atoms in the region within 30 nm from the surface layer side is 0.90 or more, the region (a) Is more easily formed. Further, in the formation of the transition metal M2 containing layer, the transition metal M2 containing layer is made to be nitrogen by, for example, using a transition metal M2 nitride or oxynitride as a raw material and introducing nitrogen during film formation. When forming as a layer containing, the region (a) is more easily formed in the mixed region. At this time, when a layer containing nitrogen is formed as the transition metal M2 containing layer, the atomic ratio of nitrogen atoms to nontransition metal M1 atoms in a region within 30 nm from the surface side of the nontransition metal M1 containing layer (N / The maximum value in the thickness direction of M1) is preferably 0.50 or more. This is because the region (a) can be formed more favorably within the above range. From the same viewpoint, when forming a layer containing nitrogen as the transition metal M2 containing layer, the atomic ratio of nitrogen atoms to nontransition metal M1 atoms in a region within 30 nm from the surface side of the nontransition metal M1 containing layer ( The maximum value in the thickness direction of N / M1) is more preferably 0.60 or more, and extremely preferably 0.90 or more. Moreover, the maximum value in the thickness direction of the atomic ratio (N / M1) of nitrogen atoms to non-transition metal M1 atoms in the region within 30 nm from the surface layer side of the non-transition metal M1 containing layer is 1.4 or less. Is preferred. Here, the reason why the preferable condition of the maximum value of the region within 30 nm from the surface layer side of the non-transition metal M1 containing layer is defined is that the coating method has a large composition distribution in the thickness direction. This is because it greatly affects the formation of the region (a). The XPS measurement analysis and the atomic composition distribution profile used here are the same as those described in the description of the atomic composition profile.

Hereinafter, the case where the non-transition metal M1 is silicon (Si) will be described as an example, but the present invention is not limited to this.

≪Silicon-containing compound≫
A layer containing Si (also referred to herein as a silicon-containing layer) can be obtained by applying and drying a coating solution containing a silicon-containing compound. Examples of the silicon-containing compound include polysiloxane, polysilsesquioxane, polysilazane, polysiloxazan, polysilane, polycarbosilane, and the like. In addition, a well-known compound can be used as polysiloxane, polysilsesquioxane, polysilazane, polysiloxazan, polysilane, and polycarbosilane. Among these, it is preferable to have at least one selected from the group consisting of a silicon-nitrogen bond, a silicon-hydrogen bond, and a silicon-silicon bond. More preferable specific examples of the silicon-containing compound include polysilazane having a silicon-nitrogen bond and silicon-hydrogen bond, polysiloxazan having a silicon-nitrogen bond, polysiloxane having a silicon-hydrogen bond, and having a silicon-hydrogen bond. Polysilsesquioxane and polysilane having a silicon-silicon bond can be preferably used. The silicon-containing compounds can be used alone or in combination of two or more.

As the silicon-containing compound, polysilazane is more preferable. Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as Si ₂ N, Si ₃ N ₄ , and both intermediate solid solutions SiO _z N _y having a bond such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer. The polysilazane is not particularly limited and a known one can be used, but it is more preferable to have a structure of the following general formula (I).

In general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. Is preferred. At this time, R ₁ , R ₂ and R ₃ may be the same or different. N is an integer and is preferably determined so that the polysilazane having the structure represented by the general formula (I) has a number average molecular weight of 150 to 150,000 g / mol. The structure represented by the general formula (I) may form a ring structure.

Among these, in the compound having the structure represented by the general formula (I), perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable. Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.

Other examples of polysilazane that can be used in the present invention are not limited to the following, and examples thereof include JP-A-5-238827, JP-A-6-122852, JP-A-6-240208, and JP-A-6-299118. No. 6, JP-A-6-306329, JP-A-7-196986) and the like.

Polysilazane may be a commercially available product. A commercially available product is generally in a solution state dissolved in an organic solvent. In this case, the commercially available product can be used as it is as the coating solution for forming the layer (B). Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by Merck Co., Ltd. .

These polysilazanes or polysilazane solutions can be used alone or in combination of two or more.

The content of polysilazane in the silicon-containing layer before the modification treatment, which will be described later, may be 100 mass% when the total mass of the non-transition metal M1 containing layer before the modification treatment is 100 mass%. When the silicon-containing layer before the modification treatment contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99.9% by mass or less, and preferably 10% by mass or more. More preferably, it is 99.5 mass% or less, More preferably, it is 10 mass% or more and 99 mass% or less, More preferably, it is 40 mass% or more and 98 mass% or less, 70 mass% or more and 97 mass% or less. % Is particularly preferably 90% by mass or more and 97% by mass or less, and most preferably 93% by mass or more and 97% by mass or less.

≪Coating liquid for forming silicon-containing layer≫
The coating liquid for forming a silicon-containing layer is a liquid containing a silicon-containing compound as an essential component. The coating solution for forming a silicon-containing layer may further contain a solvent. The solvent is not particularly limited as long as it can dissolve the silicon-containing compound, but does not include water and reactive groups (for example, hydroxyl group or amine group) that easily react with the silicon-containing compound, and silicon. An organic solvent inert to the contained compound is preferred, and an aprotic organic solvent is more preferred. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. Hydrogen solvents; Halogenated 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; Alicyclic ethers and the like Examples of ethers include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

The concentration of the silicon-containing compound in the coating solution for forming a silicon-containing layer is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass, more preferably 2 to 40% by mass.

When the silicon-containing layer is modified, the silicon-containing layer-forming coating solution preferably contains a catalyst in order to promote the modification. The catalyst is preferably a basic catalyst, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′— Amine catalysts such as tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, and Pd compounds such as propionic acid Pd And metal catalysts such as Rh compounds such as Rh acetylacetonate and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

Further, the coating solution for forming a silicon-containing layer may further contain other additives. Other additives are not particularly limited, and known additives can be used, and examples thereof include cellulose ethers, cellulose esters, natural resins, synthetic resins, and condensation resins.

≪Application method≫
As a method of applying the silicon-containing layer forming coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include 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 and the like. It is done.

The coating thickness can be appropriately set according to the preferred thickness and purpose.

After applying the coating solution, the coating film is dried. By drying the coating film, an organic solvent that can be contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable layer (B) can be obtained. The remaining solvent can be removed later.

The drying temperature of the coating film is preferably 50 to 200 ° C. For example, when a gas barrier film is used in the form of a gas barrier film and a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used, the drying temperature is the deformation of the resin substrate due to heat. In view of the above, it is preferable to set the temperature to 150 ° C. or lower. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 50 to 150 ° C., the drying time is preferably set within 30 minutes. At this time, the lower limit of the drying time is not particularly limited as long as the desired dry state can be achieved, but it is preferably, for example, 30 seconds or more. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

The coating film obtained by applying the silicon-containing layer forming coating solution may include a step of removing moisture before irradiation with vacuum ultraviolet rays or during irradiation with vacuum ultraviolet rays. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. The dew point temperature is preferably 4 ° C. or lower (temperature 25 ° C./relative humidity 25% RH), and the maintained time is preferably 1 minute or longer. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher.

≪Reformation (conversion) ≫
A coating film containing a silicon-containing compound (coating liquid for forming a silicon-containing layer) can be used as it is as a silicon-containing layer, but the resulting coating film is subjected to a modification treatment to convert it into silicon oxynitride or the like. A silicon-containing layer may be formed by performing the above. The modification method is not particularly limited, and a known method can be used, but a method of performing vacuum ultraviolet irradiation is preferable. Vacuum ultraviolet irradiation has the advantage of further improving the water vapor barrier property in a high temperature and high humidity environment. Moreover, vacuum ultraviolet irradiation has the advantage that the deterioration of the water vapor barrier property due to the environmental influence of storage over time between the formation of the silicon-containing layer and the formation of the transition metal M2 containing layer is further suppressed.

Vacuum ultraviolet irradiation is applicable to both batch processing and continuous processing, and can be selected as appropriate. For example, in the case of batch processing, it can be processed in an ultraviolet baking furnace equipped with an ultraviolet ray generation source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Further, when the object is a long film, it can be converted to ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. The time required for ultraviolet irradiation is generally from 0.1 second to 10 minutes, preferably from 0.5 second to 3 minutes, depending on the composition and concentration of the silicon-containing layer and the type of film formation target.

The modification by vacuum ultraviolet irradiation uses an optical energy of 100 to 200 nm, preferably an optical energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in a silicon-containing compound (particularly a polysilazane compound), and bonds the atoms. A method of forming a film containing silicon oxynitride at a relatively low temperature (about 200 ° C. or less) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of only photons called photon processes It is. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together.

The vacuum ultraviolet source is preferably an excimer radiator (eg, an Xe excimer lamp) having a maximum emission at about 172 nm, a low pressure mercury vapor lamp having an emission line at about 185 nm, and medium and high pressure mercury vapor having a wavelength component of 230 nm or less. A lamp, and an excimer lamp having a maximum emission at about 222 nm.

Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

Also, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. The coating film can be modified in a short time by the high energy of the active oxygen, ozone and ultraviolet radiation.

¡Excimer lamps have high light generation efficiency and can be lit with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

The vacuum ultraviolet ray may be generated by plasma formed by a gas containing at least one of CO, CO ₂ and CH ₄ .

The oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). Is more preferable. Also, the water vapor concentration during the conversion process is preferably in the range of 1,000 to 4,000 volume ppm.

As the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, it is preferable to use a dry inert gas, and more preferable to use 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 chamber and changing the flow rate ratio.

In the vacuum ultraviolet ray irradiation step, the illuminance of the vacuum ultraviolet ray on the coating surface received by the coating film is preferably 1 mW / cm ² to 10 W / cm ² , more preferably 30 mW / cm ² to 200 mW / cm ² , further preferably at ^{50mW / cm 2 ~ 160mW / cm} 2. If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that may occur in the coating film and damage to the film formation target can be reduced.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the surface of the coating film is preferably 0.1 to 10 J / cm ² , and more preferably 0.1 to 7 J / cm ² . If it is this range, generation | occurrence | production of the crack by excessive reforming and the thermal deformation of the film-forming target object can be suppressed, and productivity will improve.

The thickness of the layer containing the non-transition metal M1 formed by the coating method, including the silicon-containing layer formed by the coating method described above, is preferably 10 to 500 nm, more preferably 30 to 300 nm. preferable.

When the non-transition metal M1 containing layer is formed by a coating method, for example, a film forming raw material type (polysilazane type or the like) containing the non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, and a drying temperature. The composition and thickness of the region (a) can be controlled by adjusting one or more conditions selected from the group consisting of time, modification method, and modification conditions.

[Method of forming transition metal M2 containing layer]
The method for forming the transition metal M2 containing layer is not particularly limited, and examples thereof include a vapor phase film forming method and a coating method. Among these, from the viewpoint that the non-transition metal M1-containing layer and the transition metal M2-containing layer can be continuously formed while conveying the film formation target, and it is excellent in productivity, this is a vapor phase film formation method. It is preferable. Here, as a method of forming each layer while conveying the film formation target, for example, a roll-to-roll method may be mentioned. That is, the manufacturing method according to a preferred embodiment of the present invention is a manufacturing method including forming the transition metal M2 containing layer by a vapor deposition method.

In one embodiment of the present invention, the raw material for forming the transition metal M2 containing layer is not particularly limited as long as it is a compound derived from the transition metal M2 (a compound containing the transition metal M2 alone or the transition metal M2). Moreover, as a raw material for forming a transition metal M2 content layer, the substance (A metal simple substance, the compound containing a metal) derived from other metals may further be contained. At this time, in the raw material of the transition metal M2 containing layer, the raw material capable of forming the non-transition metal M1 containing layer, that is, the substance derived from the non-transition metal M1 (non-transition metal M1 simple substance, compound containing non-transition metal M1) May further be included. In this case, the layer classification is determined as follows. First, only the transition metal M2 containing layer is separately formed on the object to be formed under the same conditions as the production of the gas barrier film. Next, the atomic composition ratio (atm%) of the metal element contained in the constituent components and the atomic composition ratio (atm%) of the non-transition metal M2 are measured in the XPS analysis method in the same manner as the atomic composition profile of the gas barrier film described above. To measure. Then, among the metal elements contained in the constituent components in the produced layer, the layer having the maximum transition metal M2 content as the atomic composition ratio is treated as the formation of the transition metal M2 containing layer.

Film formation by sputtering has the advantage of higher film formation rate and higher productivity. Further, it is extremely high to form both the non-transition metal M1 containing layer and the transition metal M2 containing layer by the sputtering method, and in particular, to form each layer continuously by the sputtering method while conveying the film formation target. There is an advantage of having productivity.

For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The details of the sputtering method are the same as the contents described in the above section [Formation of Non-Transition Metal M1 Containing Layer] except for the contents specifically described below, and thus the description thereof is omitted here.

The type of transition metal M2 included in the target used in the sputtering method and the preferable type of transition metal M2 are the same as those of the transition metal M2 described for the region (B). Further, as the target including the transition metal M2, the same compound as the compound derived from the transition metal M2 described for the region (B) can be used. Here, the target containing the transition metal M2 is preferably a target containing an oxide of the transition metal M2 from the viewpoint of higher film formation rate and higher productivity. From the viewpoint of further improving the water vapor barrier property, an oxygen-deficient transition metal M2 oxide is more preferable. Here, as a preferable example of the target containing the transition metal M2, a commercially available oxygen-deficient niobium oxide target, a commercially available tantalum target, and the like can be given.

Here, when forming the transition metal M2 oxide film as the transition metal M2 containing layer by sputtering, for example, a mixed gas of an inert gas and an oxygen gas may be used as the process gas. The ratio of the oxygen partial pressure to the pressure is preferably 0 to 40%, more preferably 5 to 30%.

When the transition metal M2 containing layer is formed by the vapor deposition method, for example, the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas and the reactive gas during film formation, By adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation, The composition and thickness of region (a) can be controlled. Here, as a method of controlling the thicknesses of the mixed region and the region (a), a method of controlling the film formation time of the transition metal M2 containing layer is particularly preferable.

When forming the transition metal M2 containing layer by a vapor phase film forming method, it is preferable to form the film in an environment containing nitrogen. At this time, the transition metal M2 containing layer can be a film containing nitrogen, such as a nitride film or an oxynitride film. The transition metal M2 containing layer contains nitrogen, so that spontaneous diffusion of the substance at the interface between the non-transition metal M1 containing layer and the transition metal M2 containing layer, and the substance in forming the transition metal M2 containing layer By entering the non-transition metal M1-containing layer, nitrogen is easily introduced into the vicinity of the interface. As a result, in the mixed region, the existing atomic ratio (y) of the nitrogen atom to the non-transition metal M1 atom can be more easily controlled to a value within the range satisfying the formula (2). Therefore, the method for manufacturing a gas barrier film according to a preferred embodiment of the present invention is a manufacturing method in which the atmosphere of the vapor phase film forming method is an atmosphere containing nitrogen. The method for introducing nitrogen is not particularly limited. For example, when a transition metal M2 nitride film is formed as the transition metal M2 containing layer by sputtering, for example, an inert gas and a nitrogen gas are used as process gases. A mixed gas may be used. At this time, the ratio of the nitrogen partial pressure to the total pressure is preferably 10 to 90%, and more preferably 20 to 80%.

The film formation setting thickness when forming the transition metal M2 containing layer is 3 nm or more from the viewpoint of forming a sufficiently thick region (a) and obtaining a higher water vapor barrier property in a high temperature and high humidity environment. It is preferable that it is 5 nm or more. Further, since the thickness of the region (a) is saturated even if the thickness is further increased, the viewpoint of obtaining a high water vapor barrier property in a high-temperature and high-humidity environment with a thinner film thickness, and better flexibility From the viewpoint of obtaining, it is preferably 30 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less.

[Formation of mixed region by co-evaporation method]
As described above, the non-transition metal M1 containing layer and the transition metal M2 containing layer may be formed so as to further include the transition metal M2 and the non-transition metal M1, respectively. Therefore, when the non-transition metal M1 containing layer or the transition metal M2 containing layer is formed by a vapor deposition method, the mixed region may be directly formed by using a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method is, for example, a single unit using, as a sputtering target, a composite target made of an alloy containing both the non-transition metal M1 and the transition metal M2, or a composite target made of a composite oxide of the non-transition metal M1 and the transition metal M2. It can be sputter. The co-sputtering method may be, for example, multi-source simultaneous sputtering using a plurality of sputtering targets including a single element of non-transition metal M1 or its oxide and a single element of transition metal M2 or its oxide. With respect to a method for producing these sputtering targets and a method for producing a thin film made of a composite oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP Reference can be made to the descriptions in Japanese Patent Application Laid-Open No. 2013-047361. Further, when the mixed region is formed by a co-evaporation method, the region (a) may be directly formed by appropriately introducing nitrogen.

However, in the manufacturing method according to the present invention, it is better to form the non-transition metal M1 layer containing only the non-transition metal M1 and the transition metal M2 layer containing only the transition metal M2, respectively. It is preferable because it can be obtained. At this time, the reason why the effect of the present invention is better achieved is not clear in detail, but the composition of the mixed region (a), the non-transition element M1, the transition element M2 and the nitrogen atom in the mixed region (a) It is presumed that the existence state or the like is likely to become a more suitable state for the effect of the present invention.

<Gas barrier film and gas barrier film production method>
Another embodiment of the present invention is a gas barrier film having the gas barrier film according to the first embodiment of the present invention on a resin substrate. Such a gas barrier film can be produced, for example, by using the method for producing a gas barrier film according to the second embodiment of the present invention using a film formation target as a resin substrate.

In the gas barrier film according to one embodiment of the present invention, the resin base material surface on which the gas barrier film is formed is not particularly limited, and may be one side or both sides. In the case where the gas barrier film has the region (A) and the region (B) and the gas barrier film is formed on both surfaces, the region (A) and the region (B) constituting the gas barrier film. ) And the order of lamination may be the same or different on one side and the other side of the resin substrate.

[Resin substrate]
Examples of the resin base material used for the gas barrier film according to one embodiment of the present invention include a film or sheet made of a resin, and a film or sheet made of a colorless and transparent resin is preferable. Examples of the resin used for such a resin base material include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclopolyolefin; Polyamide resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Cellulose ester resin.

Among these resins, resins selected from polyester resins, polyimide resins, cyclopolyolefin resins, and polycarbonate resins are preferable, polyester resins are more preferable, and polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable. More preferred is polyethylene terephthalate (PET). Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

The resin substrate may be a single layer or a laminated structure of two or more layers. When the resin substrate has a laminated structure of two or more layers, each layer may be the same type of resin or a different type of resin.

The thickness of the resin base material can be appropriately set in consideration of stability when producing the gas barrier film of the present invention. The thickness of the resin substrate (the total thickness in the case of a laminated structure of two or more layers) is preferably in the range of 5 to 500 μm from the viewpoint that the film can be conveyed even in a vacuum.

Furthermore, when the gas barrier film according to one embodiment of the present invention is formed using the plasma CVD method, the thin film is formed while discharging through the resin substrate. In the case of a laminated structure, the total thickness) is more preferably in the range of 50 to 200 μm, and particularly preferably in the range of 50 to 100 μm.

In addition, it is preferable to subject the resin base material to a surface activation treatment for cleaning the surface of the resin base material from the viewpoint of adhesion to a gas barrier film described later. Examples of such surface activation treatment include easy adhesion treatment, corona treatment, plasma treatment, and flame treatment. Among these, easy adhesion treatment is preferable.

[Layers with various functions]
In the gas barrier film according to one embodiment of the present invention, layers having various functions can be provided.

≪Anchor coat layer≫
An anchor coat layer may be formed on the surface of the resin base on the side where the gas barrier film according to one embodiment of the present invention is formed for the purpose of improving the adhesion between the resin base and the gas barrier film.

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).

Also, the anchor coat layer can be formed by a vapor phase 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 JP-A-2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, a certain amount of gas generated from the resin substrate side is generated. An anchor coat layer can also be formed for the purpose of blocking 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 provided on the surface (one side or both sides) of the resin substrate. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

The active energy ray-curable resin 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 bond is preferably used, and the active energy ray curable resin is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. A layer containing the cured product, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. Examples of the ultraviolet curable resin include a resin composition containing a (meth) acrylate compound, a resin composition containing a (meth) acrylate compound and a mercapto compound containing a thiol group, epoxy (meth) acrylate, urethane ( Resin composition containing polyfunctional (meth) acrylate monomer such as meth) acrylate, polyester (meth) acrylate, melamine (meth) acrylate, polyether (meth) acrylate, polyethylene glycol (meth) acrylate, glycerol (meth) acrylate And a resin composition containing an amorphous fluorine-containing polymer. Here, (meth) acrylate represents acrylate or methacrylate. Moreover, as an ultraviolet curable resin, you may use a commercial item. As a commercial item, Aika Kogyo Co., Ltd. product Z731L, JSR Co., Ltd. OPSTAR (opstar) (trademark) Z7527 etc. are mentioned, for example. Moreover, you may use the commercially available resin base material in which the hard-coat layer is formed previously.

The method for forming the hard coat layer is not particularly limited, but it may be formed by a wet coating method (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 a vapor deposition method. Is preferred.

The drying temperature of the coating film when forming the hard coat layer is not particularly limited, but is preferably 40 to 120 ° C.

The active energy ray used when curing the hard coat layer is preferably ultraviolet rays.
Although it does not restrict | limit especially as an ultraviolet irradiation device, For example, a high pressure mercury lamp etc. are mentioned. Although ultraviolet irradiation conditions are not specifically limited, For example, performing under air is mentioned. The amount of ultraviolet irradiation energy is not particularly limited, but is preferably 0.3 to 5 J / cm ² .

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

The hard coat layer is not particularly limited, but a clear hard coat layer is preferably used. In addition, it is preferable that other layers, such as the above-mentioned anchor coat layer and the smooth layer mentioned later, serve as the function of a hard-coat layer.

≪Smooth layer≫
The gas barrier film according to one embodiment of the present invention may have a smooth layer between the resin base material and the gas barrier film. The smooth layer used in one embodiment of the present invention flattens the rough surface of the resin substrate where protrusions and the like are present, or fills irregularities and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin substrate. Provided for flattening. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

The photosensitive material for the smooth layer is preferably an active energy ray curable resin composition, and more preferably an ultraviolet curable resin composition. Examples of the ultraviolet curable resin composition include a resin composition containing a (meth) acrylate compound, a resin composition containing a (meth) acrylate compound and a mercapto compound having a thiol group, epoxy (meth) acrylate, and urethane. Resin compositions containing polyfunctional acrylate monomers such as (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyethylene glycol (meth) acrylate, glycerol (meth) acrylate, and amorphous fluorine-containing polymers Examples thereof include a resin composition. Here, (meth) acrylate represents acrylate or methacrylate. A commercially available product may be used as the ultraviolet curable resin, and for example, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation may be used. Examples of the OPSTAR (registered trademark) series manufactured by JSR Corporation include OPSTAR (registered trademark) Z7527. It is also possible to use any mixture of the above resin compositions, and any photosensitive material containing a reactive monomer having at least one photopolymerizable unsaturated bond 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 method for forming the smooth layer is not particularly limited, but may be formed by a wet coating method (coating method) such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as a vapor deposition method. preferable.

As the drying conditions for the smooth layer and the light irradiation conditions when the material forming the smooth layer is a photosensitive material, the same conditions as those for the hard coat layer can be employed.

In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

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

The smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601: 2001, and the 10-point average roughness Rz is preferably 10 nm or more and 30 nm or less. Within this range, even when the gas barrier film is applied in a coating form, the coating property is good even when the coating means is in contact with the smooth layer surface by a coating method such as a wire bar or a wireless bar. It is less likely to be damaged, and it is easy to smooth the unevenness after application.

<Electronic device and electronic device manufacturing method>
The performance of the gas barrier film according to one embodiment of the present invention and the gas barrier film according to one embodiment of the present invention is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. It can be preferably applied to a device. Thus, another embodiment of the present invention is an electronic device including the gas barrier film according to one embodiment of the present invention or the gas barrier film according to one embodiment of the present invention.

Still another embodiment of the present invention is to seal the functional layer surface of an electronic device with a sealing member including the gas barrier film according to one embodiment of the present invention or the gas barrier film according to one embodiment of the present invention. The manufacturing method of an electronic device containing this.

The sealing member including the gas barrier film may be a gas barrier film alone. In this case, the functional layer surface of the electronic device is sealed by forming the gas barrier film directly on the functional layer surface of the electronic device. It may be broken. Moreover, as a sealing member containing a gas barrier film, the laminated body formed by bonding a gas barrier film and a sealing resin layer is mentioned, for example. Although it does not restrict | limit especially as a sealing resin layer, For example, a thermosetting type sheet-like adhesive agent (epoxy resin) etc. are mentioned. Here, the following methods are mentioned as an example of the sealing method of the functional layer surface of an electronic device using the sealing member containing a gas barrier film or a gas barrier film. First, the adhesive forming surface of the sealing member including the gas barrier film or gas barrier film and the functional layer surface of the electronic device are continuously overlapped. Subsequently, the laminated body of a sealing member and an electronic device is arrange | positioned in a pressure-reduction apparatus, and it presses and hold | maintains the base material and sealing member which were piled up on high temperature pressure reduction conditions. Subsequently, the sample is returned to the atmospheric pressure environment, and further heated under a high temperature environment for a predetermined time to cure the adhesive.

Examples of the electronic device include an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. 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, more preferably an organic EL element, and further preferably an organic EL lighting element.

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

<Manufacture of gas barrier film having gas barrier film>
[Comparative Example 1: Production of gas barrier film 1]
(Resin base material)
As the resin substrate, a 50 μm thick polyethylene terephthalate film (Lumirror (registered trademark) U48, manufactured by Toray Industries, Inc.) with easy adhesion treatment on both sides was used. A clear hard coat layer having an antiblock function with a thickness of 0.5 μm was formed on the surface of the resin substrate opposite to the surface on which the gas barrier film was formed. That is, an ultraviolet curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied on a resin substrate so that the dry film thickness was 0.5 μm, and then dried at 80 ° C., and then under high pressure in the air. Curing was performed using a mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed as a smooth layer on the surface of the resin substrate on the side where the gas barrier film was to be formed as follows. After applying UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation to a resin base material so that the dry film thickness becomes 2 μm, it is dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a resin substrate with a clear hard coat layer was obtained. Hereinafter, in this example and the comparative example, this resin substrate with a clear hard coat layer is simply referred to as a resin substrate for convenience.

(Formation method A1 of a non-transition metal M1 content layer)
The resin substrate prepared above is set in the vacuum plasma CVD apparatus 101 shown in FIG. 4 and evacuated, and then the surface of the resin substrate on which the gas barrier film is formed (that is, a clear hard coat layer having a thickness of 2 μm) A silicon nitride film having a thickness of 50 nm was formed as a layer containing non-transition metal Si. The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The source gas was introduced into the vacuum chamber at a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 50 sccm, and a hydrogen gas flow rate of 200 sccm (sccm is cm ³ / min at 133.322 Pa). Furthermore, the resin substrate temperature was set to 100 ° C. at the start of film formation. In this way, a gas barrier film 1 was obtained.

[Comparative Example 2: Production of gas barrier film 2]
A gas barrier film 2 was obtained in the same manner as in Comparative Example 1 except that the formation method A1 of the non-transition metal M1 containing layer was changed to the following formation method A2.

(Formation method A2 of non-transition metal M1 containing layer)
A commercially available vacuum CCP (Capacitively Coupled Plasma Capacitively Coupled Plasma) -CVD apparatus was used. Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as source gases. As a power source, a high frequency power source having a frequency of 13.56 MHz was used.

The resin base material was set on the substrate holder in the vacuum chamber of the CVD apparatus, and the vacuum chamber was closed. Next, the inside of the vacuum chamber was evacuated, and the raw material gas was introduced when the pressure reached 0.1 Pa. The flow rate of silane gas was 80 sccm, the flow rate of ammonia gas was 60 sccm, the flow rate of nitrogen gas was 350 sccm, and the flow rate of hydrogen gas was 80 sccm.

After the pressure in the vacuum chamber is stabilized at 50 Pa, a plasma excitation power of 600 W is supplied from the high-frequency power source to the electrode, and the surface of the clear hard coat layer of the resin substrate is a layer containing non-transition metal Si, A silicon nitride film having a thickness of 50 nm was formed.

[Comparative Example 3: Production of gas barrier film 3]
A gas barrier film 3 was obtained in the same manner as in Comparative Example 2, except that the formation method A2 of the non-transition metal M1 containing layer was changed to the following formation method A3.

(Formation method A3 of non-transition metal M1 containing layer)
Non-transition metal M1 containing layer formation method A2 is the same except that the flow rate of silane gas is 80 sccm, the flow rate of ammonia gas is 150 sccm, the flow rate of nitrogen gas is 200 sccm, the flow rate of hydrogen gas is 170 sccm, and the plasma excitation power is 1200 W. Thus, a silicon nitride film having a thickness of 50 nm was formed as a layer containing non-transition metal Si.

[Comparative Example 4: Production of Gas Barrier Film 4]
A gas barrier film 4 was obtained in the same manner as in Comparative Example 2 except that the formation method A2 of the non-transition metal M1 containing layer was changed to the following formation method A4.

(Formation method A4 of non-transition metal M1 containing layer)
A silicon nitride film was formed in the same manner as in the formation method A2 of the non-transition metal M1 containing layer except that the thickness was 100 nm.

[Comparative Example 5: Production of gas barrier film 5]
A gas barrier film 5 was obtained in the same manner as in Comparative Example 2 except that the formation method A2 of the non-transition metal M1 containing layer was changed to the following formation method A5.

(Formation method A5 of a non-transition metal M1 content layer)
A silicon nitride film was formed in the same manner as in the formation method A2 of the non-transition metal M1-containing layer except that the thickness was 300 nm.

[Comparative Example 6: Production of gas barrier film 6]
A gas barrier film 6 was obtained in the same manner as in Comparative Example 2 except that the formation method A2 of the non-transition metal M1 containing layer was changed to the following formation method A6.

(Formation method A6 of non-transition metal M1 containing layer)
In the formation method A2 of the non-transition metal M1-containing layer, the obtained silicon nitride film is further subjected to plasma irradiation treatment with emission of light having a wavelength of 150 nm or less (105 nm, 107 nm, 121 nm) using the following apparatus and conditions. A silicon nitride film having a thickness of 50 nm was formed as a layer containing non-transition metal Si.

≪Plasma irradiation treatment≫
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: He + H ₂ (H ₂ concentration: 6 vol%),
Total pressure: 19 Pa,
Resin base material heating temperature: room temperature,
Input power density: 1.3 W / cm ² ,
Frequency: 13.56MHz,
Processing time: 60 seconds.

[Comparative Example 7: Production of gas barrier film 7]
A gas barrier film 7 was obtained in the same manner as in Comparative Example 5 except that the formation method A5 of the non-transition metal M1 containing layer was changed to the following formation method A7.

(Formation method A7 of non-transition metal M1 containing layer)
In the formation method A5 of the non-transition metal M1-containing layer, the obtained silicon nitride film was further subjected to the plasma irradiation treatment in the same manner as the plasma irradiation treatment in the non-transition metal M1-containing layer formation method A6. A silicon nitride film having a thickness of 300 nm was formed in the same manner except for the above.

[Comparative Example 8: Production of gas barrier film 8]
A gas barrier film 8 was obtained in the same manner as in Comparative Example 1 except that the formation method A1 of the non-transition metal M1 containing layer was changed to the following formation method A8.

(Formation method A8 of non-transition metal M1 containing layer)
A silicon nitride film having a thickness of 50 nm was formed as a layer containing non-transition metal Si on the surface of the resin substrate on the side on which the gas barrier film was formed, using a magnetron sputtering apparatus (Canon Anelva Co., Ltd .: Model EB1100). . At this time, a commercially available silicon target was used as the target, Ar and N ₂ were used as the process gas, and the ratio of the nitrogen partial pressure to the total pressure was 50%, and the film was formed by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. The thickness is in the range of 100 to 300 nm, data on the change in film thickness with respect to the film formation time is taken, the film formation time per unit time is calculated, and then the film formation time is set to the set thickness. It was adjusted by doing.

[Comparative Example 9: Production of gas barrier film 9]
A gas barrier film 9 was obtained in the same manner as in Comparative Example 8 except that the formation method A8 of the non-transition metal M1 containing layer was changed to the following formation method A9.

(Formation method A9 of non-transition metal M1 containing layer)
In the formation method A8 of the non-transition metal M1 containing layer, the obtained silicon nitride film was subjected to the plasma irradiation treatment by the same method as the plasma irradiation treatment in the formation method A6 of the non-transition metal M1 containing layer. Similarly, a silicon nitride film having a thickness of 50 nm was formed as a layer containing non-transition metal Si.

[Comparative Example 10: Production of gas barrier film 10]
After the formation method A1 of the non-transition metal M1 containing layer, the laminate of the non-transition metal M1 containing layer and the resin base material is transported, and the following transition metal M2 containing layer formation method B1 on the surface of the obtained silicon nitride film Then, an oxide Nb film was formed. Except for this, a gas barrier film 10 was obtained in the same manner as in Comparative Example 1.

(Formation method B1 of transition metal M2 containing layer)
On the surface of the silicon nitride film obtained by the formation method A1 of the non-transition metal M1 containing layer, a magnetron sputtering apparatus (manufactured by Canon Anelva Co., Ltd .: model EB1100) is used to oxidize the layer containing the transition metal M2 to a thickness of 6 nm. A niobium film was formed. At this time, a commercially available oxygen-deficient niobium oxide target (composition is Nb ₁₂ O ₂₉ ) is used as the target, Ar and O ₂ are used as the process gas, and the ratio of the oxygen partial pressure to the total pressure is 12%. Film formation was performed by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. The thickness is in the range of 100 to 300 nm, data on the change in thickness with respect to the film formation time is taken, the film formation time per unit time is calculated, and then the film formation time is set to the set thickness. It was adjusted by doing.

[Comparative Example 11: Production of gas barrier film 11]
A gas barrier film 11 was obtained in the same manner as in Comparative Example 10 except that the formation method B1 of the transition metal M2 containing layer was changed to the following formation method B2.

(Formation method B2 of transition metal M2 containing layer)
A niobium oxide film was formed in the same manner as in the formation method B1 of the transition metal M2 containing layer except that the thickness was 10 nm.

[Example 1: Production of gas barrier film 12]
After the formation method A2 of the non-transition metal M1-containing layer, the laminate of the non-transition metal M1-containing layer and the resin base material is transported, and the above-described transition metal M2-containing layer formation method B1 on the surface of the obtained silicon nitride film The niobium oxide film was further formed by Except this, it carried out similarly to the comparative example 2, and obtained the gas-barrier film 12.

[Example 2: Production of gas barrier film 13]
After the formation method A3 of the non-transition metal M1 containing layer, the laminate of the non-transition metal M1 containing layer and the resin base material is transported, and the above-mentioned transition metal M2 containing layer formation method B1 on the surface of the obtained silicon nitride film The niobium oxide film was further formed by Except this, it carried out similarly to the comparative example 3, and obtained the gas-barrier film 13.

[Example 3: Production of gas barrier film 14]
After the formation method A3 of the non-transition metal M1 containing layer, the laminate of the non-transition metal M1 containing layer and the resin base material is transported, and the above-described transition metal M2 containing layer formation method B2 on the surface of the obtained silicon nitride film The niobium oxide film was further formed by Except for this, a gas barrier film 14 was obtained in the same manner as in Comparative Example 3.

[Example 4: Production of gas barrier film 15]
After the formation method A8 of the non-transition metal M1-containing layer, the laminate of the non-transition metal M1-containing layer and the resin base material is transported, and the above-described transition metal M2-containing layer formation method B1 on the surface of the obtained silicon nitride film Then, a layer containing a transition metal Nb was further formed. Except this, it carried out similarly to the comparative example 8, and obtained the gas barrier film 15 which has a gas barrier film obtained by forming the layer containing a transition metal Nb on the surface of the layer containing non-transition metal Si. .

[Example 5: Production of gas barrier film 16]
A gas barrier film 16 was obtained in the same manner as in Example 2 except that the formation method B1 of the transition metal M2 containing layer was changed to the formation method of the following formation method layer B3.

(Formation method B3 of transition metal M2 containing layer)
In the formation method B1 of the transition metal M2 containing layer, a commercially available tantalum target (Ta) is used as the target, and the tantalum oxide film having a thickness of 6 nm is similarly used except that the ratio of the oxygen partial pressure to the total pressure is 18%. Formed.

[Example 6: Production of gas barrier film 17]
A gas barrier film 17 was obtained in the same manner as in Comparative Example 10 except that the formation method B1 of the transition metal M2 containing layer was changed to the following formation method B4.

(Formation method B4 of transition metal M2 containing layer)
In the formation method B1 of the transition metal M2 containing layer, the same except that nitrogen gas was introduced into the process gas, Ar and N ₂ were used as the process gas, and the ratio of the nitrogen partial pressure to the total pressure was 50% Thus, a niobium oxynitride (niobium oxynitride) film having a thickness of 6 nm was formed as a layer containing the transition metal M2.

[Comparative Example 12: Production of gas barrier film 18]
A gas barrier film 18 was obtained in the same manner as in Example 2 except that the formation method B1 of the transition metal M2 containing layer was changed to the following formation method B5.

(Transition metal M2-containing layer B5)
A niobium oxynitride film was formed in the same manner as in the formation method B1 of the transition metal M2-containing layer, except that the thickness was 2 nm.

[Comparative Example 13: Production of gas barrier film 19]
A gas barrier film 19 was obtained in the same manner as in Comparative Example 1 except that the formation method A1 of the non-transition metal M1 containing layer was changed to the following formation method A10.

(Formation method A10 of non-transition metal M1 containing layer)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (Merck Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH)) 5 parts by weight per 100 parts by weight of perhydropolysilazane and a dibutyl ether solution containing 20% by weight of perhydropolysilazane (manufactured by Merck & Co., NAX120-20) mixed at a ratio of 4: 1 (mass ratio) Further, it was diluted with dibutyl ether so that the concentration became 3% by mass to prepare a coating solution containing non-transition metal Si. The coating solution was prepared in a glove box.

The coating liquid was applied to the surface of the resin substrate on the side where the gas barrier film was to be formed by spin coating so that the dry film thickness was 100 nm, and dried at 80 ° C. for 2 minutes. Next, vacuum ultraviolet irradiation treatment was performed on the dried coating film using the vacuum ultraviolet irradiation apparatus of FIG. 5 having an Xe excimer lamp with a wavelength of 172 nm under the condition that the irradiation energy amount was 6.0 J / cm ² . At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. Further, the stage temperature at which the sample (the gas barrier film before the modification treatment) was set was 80 ° C.

In FIG. 5, reference numeral 1 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. 2 is an Xe excimer lamp having a double tube structure that irradiates 172 nm vacuum ultraviolet light (excimer lamp light intensity: 130 mW / cm ² ), 3 is an excimer lamp holder that also serves as an external electrode, and 4 is a sample stage. The sample stage 4 can reciprocate horizontally in the apparatus chamber 1 at a predetermined speed (V in FIG. 5) by a moving means (not shown). The sample stage 4 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 5 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 6 denotes a light-shielding plate which prevents the application of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 2.

Here, the energy applied to the surface of the sample coating layer by the vacuum ultraviolet irradiation treatment was measured using a 172 nm sensor head using a UV integrating photometer (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd. In measurement, the sensor head is placed at the center of the sample stage 4 so that the shortest distance between the tube surface of the Xe excimer lamp 2 and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 1 is a vacuum ultraviolet ray. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the irradiation step, and measurement was performed by moving the sample stage 4 at a speed of 0.5 m / min. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 2, an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement. Based on the irradiation energy obtained by this measurement, the irradiation energy amount was adjusted by adjusting the moving speed of the sample stage. The vacuum ultraviolet irradiation was performed after aging for 10 minutes.

Thus, a polysilazane modified film including a silicon oxynitride film having a thickness of 100 nm was formed as a layer containing non-transition metal Si on the surface of the resin base on the side where the gas barrier film was formed. When the composition distribution in the thickness direction of this layer was measured by XPS analysis to be described later, the N / Si ratio of this layer was 0.1 as the average value in the thickness direction of the entire layer. However, the portion of the polysilazane modified film having a thickness of about 30 nm on the surface layer side opposite to the resin substrate side is silicon oxynitride (silicon oxynitride) in which nitrogen (N) contained in the original polysilazane remains. The maximum value of the N / Si ratio of the film was 0.6.

[Example 7: Production of gas barrier film 20]
A niobium oxynitride film was further formed on the surface of the polysilazane modified film obtained by the formation method A10 of the non-transition metal M1-containing layer by the formation method B4 of the transition metal M2-containing layer. Except for this, a gas barrier film 20 was obtained in the same manner as in Comparative Example 13.

The production conditions of the gas barrier film in the gas barrier films 1 to 20 are shown in Table 1 below.

<Evaluation of gas barrier film>
[Measurement of composition distribution in thickness direction of gas barrier film]
The composition distribution profile in the thickness direction of the gas barrier film was measured by XPS analysis. XPS analysis conditions are as follows.

(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 for 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 non-transition metal M1 (silicon (Si)), transition metal M2 (niobium (Nb), tantalum (Ta)), oxygen (O), nitrogen (N), and carbon (C).

From the measurement results, the presence or absence of the region (A) containing the non-transition metal M1 as the main component of the metal element, the region (B) containing the transition metal M2 as the main component of the metal element, the mixed region, and the region (a) Judged. Further, from the measurement results, the N / Si ratio (average value in the thickness direction) of the non-transition metal M1 containing layer, the presence / absence of the mixed region, and the composition of the mixed region are expressed as M1M2 _x N _y (0.02 ≦ x ≦ 49, y The maximum value (y maximum value) of the atomic ratio of nitrogen atoms to the non-transition metal M1 atoms and the thickness of the region (a) when represented by ≧ 0) were obtained.

Here, the presence or absence of the mixed region is determined by satisfying the elemental composition in which the ratio of the atomic ratio of the transition metal M2 to the nontransition metal M1 in the thickness direction of the gas barrier film is in the range of 0.02 to 49. When it has the area | region to do, it shall have a mixed area | region.

In addition, the determination of the presence or absence of the region (a) has the region (a) when the composition is expressed by M1M2 _x N _y and the region satisfies the following formula (1) and the following formula (2). It was supposed to be.

In this evaluation, the N / Si ratio (average value in the thickness direction) of the non-transition metal M1-containing layers of the gas barrier films 10 to 18 and 20 is determined except that the non-transition metal M2 layer is not formed. A measurement sample having only a non-transition metal M1-containing layer on a resin base material formed by the same method as those of these films was prepared, and the measured value was used.

These results are shown in Table 2 below. Note that the maximum y value of the gas barrier films according to the gas barrier films 10 to 18 and 20 (Examples 1 to 7) is 0.2 ≦ x ≦ 3 when the composition of the mixed region is represented by M1M2 _x N _y. It was within the range of 0.0.

[Evaluation of water vapor permeability (water vapor barrier property) of gas barrier membrane (Ca method)]
(Production of water vapor permeability evaluation cell)
According to the following measuring method, the water vapor permeability of each gas barrier film having a gas barrier film was evaluated under three conditions. Here, since two gas barrier films are required to produce one type of water vapor permeability evaluation cell, six gas barrier films are prepared for evaluation under three types of conditions. did.

A water vapor permeability evaluation cell was prepared as follows. First, after cleaning the surface of the gas barrier film of one gas barrier film with UV, a thermosetting sheet-like adhesive (epoxy resin) having a thickness of 20 μm was bonded to the surface of the gas barrier film as a sealing resin layer. . Next, the obtained laminate of the gas barrier film and the sealing resin layer was punched out to a size of 50 mm × 50 mm, and then put into a glove box, followed by drying treatment for 24 hours. Further, after punching out another gas barrier film to a size of 50 mm × 50 mm, the surface of the gas barrier film included in the gas barrier film was subjected to UV cleaning. Subsequently, Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center position of the gas-barrier film | membrane surface which a gas-barrier film has using the vacuum evaporation apparatus by an LS technology company. Here, the thickness of Ca was 80 nm. Subsequently, the gas barrier film on which Ca is vapor-deposited is taken out into the glove box, and the sealing resin layer surface of the laminate of the punched gas barrier film and the sealing resin layer, and the gas barrier property on which Ca is vapor-deposited. It arrange | positioned so that the Ca vapor deposition surface of a film might touch, and it adhere | attached by the vacuum lamination. Here, the vacuum lamination is performed in a state in which a laminated body (a laminated body of a gas barrier film and a sealing resin layer and a gas barrier film on which Ca is vapor-deposited) is heated at 110 ° C. It was. Then, on the hot plate set at 110 ° C. the laminated body bonded by vacuum lamination, the gas barrier film side to which the sealing resin layer of the laminated body is bonded is placed down and cured for 30 minutes. A cell for evaluating water vapor permeability was prepared.

For the evaluation under three kinds of conditions, after preparing three water vapor permeability evaluation cells by the above method, pretreatment necessary for the evaluation of each condition was performed.

<< Condition 1: Standard >>
Since the water vapor permeability evaluation cell was used as it was, no pretreatment was performed.

<< Condition 2: Bending process 1 >>
A bending process was performed on the water vapor permeability evaluation cell. First, a metal cylindrical member having a diameter of 10 mm and a length of 100 mm was prepared. Next, the central part of the water vapor permeability evaluation cell was wound around the cylindrical member by 180 ° so that the cylindrical member and the film surface of the gas barrier film on which the sealing resin layer of the water vapor permeability evaluation cell was bonded. . Then, the central portion of the water vapor permeability evaluation cell is 180 ° to the cylindrical member so that the cylindrical surface and the film surface of the gas barrier film on which Ca, which is the opposite surface of the water vapor permeability evaluation cell, is deposited. I wrapped it. The bending process was repeated 100 times, with the winding operation on the two film surfaces of the water vapor permeability evaluation cell for this cylindrical member as one bending process.

<< Condition 3: Bending process 2 >>
The surface of the gas barrier film on which the sealing resin layer of the water vapor permeability evaluation cell was bonded was punched into a size of 50 mm × 50 mm using a commercially available transparent adhesive sheet (thickness 20 μm), and the thickness 125 μm. After the PET film was bonded, the same bending treatment as the bending treatment 1 was performed. In the bending process 2, the PET film is bonded to one side, so that the position of each gas barrier film of the two gas barrier films greatly deviates from the center of bending during the bending process. For this reason, the bending process 2 is a process in which the damage to the gas barrier film is larger than that of the bending process 1.

(Treatment in high temperature and high humidity environment)
After performing the pre-treatment necessary for the evaluation of each condition, the water vapor permeability of the gas barrier film possessed by each gas barrier film is obtained by subjecting the water vapor permeability evaluation cell to a time-dependent treatment in a high temperature and high humidity environment. evaluated. Here, the cell for evaluating water vapor permeability subjected to the bending treatment 2 under the above condition 3 was subjected to a aging treatment in a high-temperature and high-humidity environment after peeling off the transparent adhesive sheet and the PET film. Specifically, the water vapor permeability is based on the following index according to the degree of decrease in the transmission density from the initial transmission density with respect to the storage time when the water vapor permeability evaluation cell is stored in an environment of 85 ° C. and 85% RH. Evaluation was based on rank. For the transmission density measurement, a black and white transmission density meter TM-5 manufactured by Konica Minolta Co., Ltd. was used, and measurement was performed at any four points in the cell, and the average value was calculated. Here, the concentration reduction of 100% represents the transmission concentration when a Ca evaluation cell is produced without performing Ca deposition. It should be noted that rank 8 or higher represents extremely excellent characteristics;
10: Less than 2% decrease in concentration at 200 hours,
9: 2% or more and less than 5% in 200 hours
8: Concentration drop from 5% to less than 10% in 200 hours,
7: 10% or more and less than 20% decrease in density in 200 hours,
6: 20% or more and less than 50% concentration decrease in 200 hours,
5: 50% or more and less than 80% concentration decrease in 200 hours,
4: Less than 80% decrease in concentration at 100 hours, 80% or more decrease in concentration at 200 hours,
3: Less than 80% decrease in density at 50 hours, 80% or more decrease in density at 100 hours,
2: Density drop is less than 80% in 20 hours, density drop is 80% or more in 50 hours,
1: Concentration drop is 80% or more in 20 hours,
The results of water vapor permeability evaluation are shown in Table 3 below.

From the above results, the gas barrier film of the example having the gas barrier film according to the present invention is extremely excellent in bending as compared with the gas barrier film of the comparative example having the gas barrier film having a configuration outside the scope of the present invention. It was confirmed that the water vapor barrier property and the remarkably high water vapor barrier property in a high temperature and high humidity environment are compatible.

Among the gas barrier film manufacturing methods produced above, gas barrier films 12 to 17 in which a non-transition metal M1-containing layer and a non-transition metal M2-containing layer are continuously formed by a vapor deposition method (Examples) The production methods 1 to 6) were excellent in productivity. Among these, the gas barrier film 15 (Example 4) in which the non-transition metal M1 containing layer and the non-transition metal M2 containing layer are continuously formed by sputtering is not changed. In particular, the film formation was possible, so that the productivity was particularly excellent.

<Durability evaluation of organic EL lighting elements>
Using the organic EL lighting element produced as described below, dark spot evaluation was performed after aging in a high temperature and high humidity environment.

[Manufacture of gas barrier film for comparative sealing member]
(Manufacture of gas barrier film 21 for comparative sealing member)
In the production of the gas barrier film 3, the coating liquid for forming an organic film obtained by mixing the following was dried on the surface of the silicon nitride film having a thickness of 50 nm obtained by the formation method A3 of the non-transition metal M1-containing layer. It apply | coated so that latter thickness might be set to 1000 nm, and it dried at 80 degreeC and obtained the coating film. Subsequently, the coating film was cured by irradiating with ultraviolet rays at an irradiation energy of 0.5 J / cm ² using a high-pressure mercury lamp in the atmosphere to form an organic film. Subsequently, a silicon nitride film having a thickness of 50 nm was formed under the same conditions as in the non-transition metal M1-containing layer formation method A3. Thus, a gas barrier film 21 having a gas barrier film obtained by forming a silicon nitride film / organic film / silicon nitride film in this order was obtained. And about the gas barrier film 21, the composition distribution of the thickness direction of a gas barrier film was measured similarly to other gas barrier films.

≪Coating liquid for organic film formation≫
Polymerizable compound: 50 parts by mass of trimethylolpropane triacrylate,
Polymerization initiator: ESACURE (registered trademark) KTO46 (manufactured by Lamberti) 1 part by mass,
Silane coupling agent: KBM-5013 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts by mass,
Surfactant: BYK (registered trademark) 378 (manufactured by Big Chemie Japan Co., Ltd.) 0.5 part by mass,
400 parts by mass of methyl ethyl ketone.

(Manufacture of gas barrier film 22 for comparative sealing member)
In the production of the gas barrier film 21, an organic film having a thickness of 1000 nm and a silicon nitride film having a thickness of 50 nm were further laminated in the same manner as the organic film forming method and the silicon nitride film forming method. Thus, a gas barrier film 22 having a gas barrier film obtained by forming a silicon nitride film / organic film / silicon nitride film / organic film / silicon nitride film in this order was obtained. And about the gas barrier film 22, the composition distribution of the thickness direction of a gas barrier film was measured like other gas barrier films.

[Production of organic EL lighting elements]
Using a non-alkali glass plate (thickness 0.7 mm) as a base material, and using the

gas barrier films

3, 13, 14, 18, 21, and 22 prepared above as a sealing member, a method as shown below Thus, bottom emission type organic EL lighting elements 101 to 106 were fabricated so that the area of the light emitting region was 5 cm × 5 cm.

(Formation of underlayer and first electrode)
A sufficiently washed alkali-free glass plate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, the following compound 118 is placed in a resistance heating boat made of tungsten, and these substrate holder and the resistance heating boat are vacuum deposition apparatus. In the first vacuum chamber. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after reducing the pressure in the first vacuum tank of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The underlayer of the first electrode was provided with a thickness of 10 nm.

Then, the base material formed up to the base layer was transferred to the second vacuum chamber while being vacuumed, and after the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. Thus, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

(Organic functional layer to second electrode)
Subsequently, the pressure was reduced to a vacuum degree of 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A transport layer (HTL) was provided.

Next, the following compound A-3 (blue light emitting dopant) and the following compound H-1 (host compound) are added so that the compound A-3 is linearly 35% by mass to 5% by mass with respect to the film thickness. The vapor deposition rate was changed depending on the location, and the vapor deposition rate was changed depending on the location so that the compound H-1 was from 65% by mass to 95% by mass, and the light emitting layer was formed by co-evaporation to a thickness of 70 nm.

Thereafter, the following compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and further potassium fluoride (KF) was formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.

(Solid sealing)
Next, a sealing member was prepared by bonding a thermosetting sheet-like adhesive (epoxy resin) with a thickness of 20 μm as a sealing resin layer to the surface of the gas barrier film of the produced gas barrier film. Using this sealing member, the sample up to the second electrode was overlaid. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the ends of the lead electrodes of the first electrode and the second electrode were exposed.

Next, the sample was placed in a decompression device, and pressed at 90 ° C. under a reduced pressure of 0.1 MPa, pressed against the superposed base material and the sealing member, and held for 5 minutes. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less, in accordance with JIS B 9920: 2002. The measured cleanliness is class 100, the dew point temperature is −80 ° C. or less, and the oxygen concentration is 0. It was performed at an atmospheric pressure of 8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

In this way, an organic EL lighting element having a light emitting region area of 5 cm × 5 cm was manufactured.

In addition, each gas barrier film used for preparation of the sealing member in each organic EL lighting element is shown in Table 4 below.

[Dark spot (DS) evaluation)
(Initial dark spot evaluation)
The organic EL lighting element was caused to emit light, and the light emission state was photographed to obtain a high-resolution digital image equivalent to 10 μm per pixel. Non-light emitting points of 4 pixels or more were recorded as dark spots, and the generation position (center position) was recorded as the pixel position.

(Forced deterioration dark spot and delayed occurrence dark spot evaluation)
After the evaluation of the initial dark spot, the organic EL lighting element was stored for 300 hours in an environment of 85 ° C. and 85% RH. Thereafter, the organic EL lighting element was caused to emit light, and the number of dark spots having a circle-equivalent diameter of 200 μm or more was determined, and this was evaluated as a forced deterioration dark spot with a rank based on the following index. Further, when there was a dark spot of 200 μm or more generated at a position not recorded as an initial dark spot, it was determined that there was a delayed dark spot. It should be noted that the dark spot evaluation represents extremely excellent characteristics in that the number of dark spots is rank 5 and there is no delayed dark spot;
5: 0-9,
4: 10-19 pieces,
3: 20-29,
2: 30-49,
1:50 or more,
These results are shown in Table 4 below.

From the above results, the gas barrier film of the example having the gas barrier film according to the present invention can achieve a high level of water vapor barrier property required for an organic EL element or the like, and dark spots are generated with a delay. It was confirmed that this can be suppressed. On the other hand, in the gas barrier film of the comparative example having a gas barrier film having a configuration outside the scope of the present invention, the water vapor barrier property in a high-temperature and high-humidity environment is inferior to the gas barrier film of the example, or the dark spot is delayed. It was confirmed that it cannot be suppressed.

This application is based on Japanese Patent Application No. 2016-148996 filed on July 28, 2016, the disclosure of which is incorporated by reference in its entirety.

1 equipment chamber,
2 Xe excimer lamp having a double tube structure for irradiating vacuum ultraviolet rays of 172 nm,
3 Excimer lamp holder that also serves as an external electrode,
4 Sample stage,
5 Sample on which a polysilazane compound coating layer is formed,
6 Shading plate,
V Sample stage moving speed,
10, 10 ′ Laminate structure of gas barrier film to be formed on

film formation object

11, 110 Film formation object,
12 Non-transition metal M1 containing layer 13 Transition metal M2 containing layer,
101 vacuum plasma CVD apparatus,
102 vacuum chamber,
103 cathode electrode,
105 susceptors,
106 heat medium circulation system,
107 vacuum exhaust system,
108 gas introduction system,
109 high frequency power supply,
160 Heating and cooling device.

Claims

In the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction, a region satisfying the following formula (1) and the following formula (2) when the composition is represented by M1M2 x N y (a) Having a gas barrier film;
A region (A) containing the non-transition metal M1 as the main component of the metal element and a region (B) containing the transition metal M2 as the main component of the metal element in the thickness direction, the region (A) The gas barrier film according to claim 1, wherein the region (B) is in contact.
The gas barrier film according to claim 1 or 2, wherein the non-transition metal M1 is Si.
The gas barrier film according to any one of claims 1 to 3, wherein the transition metal M2 is at least one metal selected from the group consisting of Nb, Ta and V.
The gas barrier film according to any one of claims 1 to 4, wherein the thickness of the region (a) is 5 nm or more.
A gas barrier film having the gas barrier film according to any one of claims 1 to 5 on a resin substrate.
An electronic device comprising the gas barrier film according to any one of claims 1 to 5 or the gas barrier film according to claim 6.
Forming a non-transition metal M1 containing layer containing the non-transition metal M1 as the main component of the metal element and a transition metal M2 containing layer containing the transition metal M2 as the main component of the metal element in contact with each other; A method for producing a gas barrier film,
In the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction of the gas barrier film, the following formula (1) and the following formula (2) are satisfied when the composition is represented by M1M2 x N y A method for producing a gas barrier film having a region (a) to be treated;
The method for producing a gas barrier film according to claim 8, wherein the transition metal M2 containing layer is formed by a vapor deposition method.
The method for producing a gas barrier film according to claim 9, wherein the atmosphere of the vapor deposition method is an atmosphere containing nitrogen.
The method for producing a gas barrier film according to any one of claims 8 to 10, wherein the non-transition metal M1-containing layer is formed by a vapor deposition method.