JPWO2018021021A1 - Gas barrier film, gas barrier film using the same, electronic device using the same, and method for producing gas barrier film - Google Patents

Abstract

The present invention provides a means capable of achieving both excellent flexibility and high water vapor barrier properties in a high temperature and high humidity environment in a gas barrier film. In the present invention, in the atomic composition distribution profile obtained when performing XPS composition analysis in the thickness direction, a region (a) satisfying the following formula (1) and the following formula (2) when the composition is indicated by M1M2xNy The present invention relates to a gas barrier film having

Description

  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 of manufacturing the gas barrier film.

In 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 as a substrate film or a sealing film is used . As a gas barrier film to be used for such applications, a high water vapor barrier property of 10 ^-6 g / (m ² · 24 h) level in water vapor transmission rate (WVTR) is required. Although both gas barrier films are known as single-layer films and laminated films, representative gas barrier films currently under investigation for the purpose of achieving high barrier properties include, for example, silicon oxide films and silicon nitride films. And an alternate multilayer stack of a silicon nitride film and an organic film, and the like.

As a method of forming each film included in the gas barrier film or the gas barrier film having a laminated structure, vapor phase film forming methods such as a vapor deposition method, a sputtering method, and a CVD method are known. Moreover, in recent years, a manufacturing method of forming a gas barrier film by applying energy to a precursor layer formed by applying a solution on a substrate has also been studied. Among these, as a method of achieving a water vapor barrier property at a level of 10 ^-6 g / (m ² · 24 h), a method of forming an inorganic film having a thickness of 1 μm or more by CVD is generally used. . However, an inorganic film having a thickness of 1 μm or more has a problem that a crack is generated at the time of bending, so that application to the flexible device as described above is difficult. Also, due to the configuration of the alternating multilayer film, the thickness tends to be further increased. From this, it is required to reduce the film thickness while maintaining high water vapor barrier properties.

  Here, the alternate multilayer laminated film achieves an apparently low water vapor permeability, that is, high water vapor barrier properties, by extremely delaying the time for water vapor to permeate through the gas barrier layer by the maze effect formed by the laminated structure. It is thought that For this reason, in the organic EL element using the alternate multilayer laminated film as a sealing application, light emission defects such as dark spots are not confirmed in the initial light emission test, but the dark spots are delayed after the acceleration test under high temperature and high humidity environment with time It may occur. From this, a gas barrier film having a water vapor barrier property that is not high in appearance but is truly high is also required to suppress light emission defects not confirmed in the initial light emission inspection and to improve the durability of the device.

In the presence of such requirements, technological developments are in progress to form inorganic films having truly high water vapor barrier properties. For example, Japanese Patent Application Laid-Open No. 2012-149278 includes a step of irradiating a film surface with light having a wavelength of 150 nm or less after depositing a dry deposited film containing at least a silicon atom and a nitrogen atom on a substrate by a dry method. And methods of making silicon-containing films are disclosed. According to the document, in the silicon-containing film produced by this method, that is, the gas barrier film, the dense Si-N-Si bond, which is the basis of the Si ₃ N ₄ structure, is formed more in the modified region and higher It is said to exhibit water vapor barrier properties and moisture and heat resistance.

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

  Therefore, an object of the present invention is to provide a 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 problems 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 performing XPS composition analysis in the thickness direction, a region (a) satisfying the following formula (1) and the following formula (2) when the composition is indicated by M1M2 _x N _y It is a gas barrier film 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 be in contact with each other,
In the thickness direction, it has a region (A) containing a non-transition metal M1 as a main component of the metal element and a region (B) containing a transition metal M2 as a main component of the metal element,
The area (A) and the area (B) are in contact with each other,
In the atomic composition distribution profile obtained when the XPS composition analysis is performed in the thickness direction of the gas barrier film, when the composition is represented by M1M2 _x N _y , the following formula (1) and the following formula (2) are satisfied (A), which is a method for producing a gas barrier film.

It is a typical graph for demonstrating an elemental profile and a mixing area | region when the composition distribution of the non-transition metal M1 and the transition metal M2 in the gas barrier film 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 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 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 device used in the Example.

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

  Also, the dimensional proportions of the drawings are exaggerated for the convenience of the description, and may differ from the actual proportions. In the description of the drawings, the same elements will be denoted by the same reference symbols, without redundant description.

<Gas barrier film>
The gas barrier film according to the first embodiment 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 a region (a) satisfying the following formula (2).

In the present specification, “the composition is represented 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. Region (a) may contain atoms other than these.

  According to the first aspect of the present invention, it is possible to provide a 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. As used herein, “water vapor barrier property in a high temperature and high humidity environment” means that the permeation of water vapor is suppressed to an extremely high level even when an accelerated test is conducted, that is, the water vapor barrier property is significantly high. It also indicates to indicate. Further, the term "flexibility" as used herein means that a high water vapor barrier property in a high temperature and high humidity environment is maintained even at the time of bending.

The present inventor estimates the mechanism by which the above configuration solves the problem as follows. First, the gas barrier film according to the first embodiment of the present invention includes a region (a) in which M 1 M 2 _x N _y has a specific composition in the mixed region. The presence of the mixed region including such a region causes the composition to change continuously or stepwise in the thickness direction of the gas barrier film. Therefore, the mixed region can suppress stress concentration, and the excellent flexibility of the gas barrier film can be realized. Although the mechanism of high water vapor barrier expression in high temperature and high humidity environment is not clear, in the region (a), the compound derived from non transition metal M1 and the compound derived from transition metal M2 mutually chemically bond It is speculated that they form a high density region by physically bonding or by intermolecular interaction or the like. And it is estimated that high-density area expresses high water vapor barrier property, and, as a result, water vapor barrier property in high temperature high humidity environment which is an accelerated test under high temperature high humidity environment aging improves. The above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention.

  Hereinafter, although each area | region which comprises a gas barrier film is demonstrated, the definition of the technical term used is demonstrated previously.

  In the present specification, the “region” means that the gas barrier film has a constant or arbitrary thickness in a plane substantially perpendicular to the thickness direction of the gas barrier film (ie, a plane parallel to the outermost surface of the gas barrier film). Within the three-dimensional range (area) between the two opposing faces formed when dividing in the vertical direction, and the composition of the component in the area is gradually constant even though it is constant in the thickness direction It may be changing.

  The "component" as used in this-application specification means the compound or the single-piece | unit of a metal or a nonmetal which comprises the specific area | region of a gas barrier film. Moreover, the "main component" as used in the field of this invention means the component whose content rate is the largest as atomic composition ratio. For example, the term "main component of metal element" refers to a metal element having a maximum content as an atomic composition ratio among metal elements contained in the component.

The gas barrier properties of the gas barrier film according to one embodiment of the present invention were based on JIS K 7126-1987 when calculated with a laminate in which the gas barrier film was 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, and less than 1 × 10 ⁻⁵ ml / (m ² · 24 h · atm) It is more preferable that it is 1 × 10 ⁻⁶ ml / (m ² · 24 h · atm) or less (lower limit: 0 ml / (m ² · 24 h · atm)). Also, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the method according to JIS K 7129-1992 is 1 × 10 ⁻³ g / (m ² ··· 24h) It is preferable that it is the high water vapor barrier property of the following, It is more preferable that it is less than 1 × 10 ⁻⁵ g / (m ² · 24 h), and 1 × 10 ⁻⁶ g / (m ² · 24 h) or less It is more preferable that there exist (lower limit 0 g / m ² · 24 h).

[Atom composition profile]
The gas barrier film according to one aspect of the present invention essentially includes a non-transition metal M1, a transition metal M2 and nitrogen. The gas barrier film according to an embodiment of the present invention preferably contains only the non-transition metal M1 and the transition metal M2 as metal elements. The inclusion 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 described below. .

(XPS analysis conditions)
The mixed region, the region (a), the region (A) and the region (B) of the gas barrier film according to one embodiment of the present invention, the composition distribution in these regions, the thickness of each region, etc. It can be determined by measurement by X-ray Photoelectron Spectroscopy (abbreviation: XPS) which will be described in detail.

  Hereinafter, the measuring method of each area | region by XPS analysis is demonstrated.

  Specifically, 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 a non-transition metal M1 (for example, silicon (Si) etc.) 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. by X-ray photoelectron spectroscopy The measurement can be made by sequentially performing surface composition analysis while exposing the inside from the surface of the gas barrier film by using measurement and rare gas ion sputtering such as argon in combination.

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 addition, in the distribution curve of the element in which the horizontal axis represents the etching time as described above, the etching time generally correlates 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 measurement of the XPS depth profile can be adopted as “the distance in the thickness direction”. Further, 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 sec (SiO ₂ thermal oxide film equivalent value).

  Below, an example of the specific conditions of the XPS analysis applicable to composition analysis of the gas barrier film which concerns on one form of this invention is shown.

Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: monochromated Al-Kα
Sputtering ion: Ar (2 keV)
・ Depth profile: The measurement is repeated at predetermined thickness intervals with SiO ₂ equivalent sputter thickness to obtain a depth profile in the depth direction ・ Quantification: The background is determined by the Shirley method, and the relative sensitivity coefficient is obtained from the obtained peak area Determine using the method. For data processing, MultiPak manufactured by ULVAC-PHI, Inc. was used. Elements to be analyzed include non-transition metals M1 (eg, silicon (Si)), transition metals M2 (eg, niobium (Nb), tantalum (Ta), etc.), oxygen (O), nitrogen (N), carbon (C). In addition, in this measurement, you may analyze also about another element, for example, another metal element, as needed.

  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 embodiment described later, the measurement resolution of the depth profile is 1 nm.

  Next, each area will be described in detail.

[Mixed region]
In the gas barrier film according to one aspect of the present invention, the atomic ratio of the transition metal M2 to the non-transition metal M1 is 0 in the atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction. It has a mixed region which is a region satisfying the elemental composition in the range of .02-49.

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

  FIG. 1 shows 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 (left end of graph). The horizontal axis represents the sputtering depth (thickness: nm), and the vertical axis represents the content (atm%) of the non-transition metal M1 and the transition metal M2. The dotted line indicates the content of non-transition metal M1, and the solid line indicates the content of transition metal M2. From the right side of the graph, a region (A) region having an elemental composition mainly composed of non-transition metal M1 (for example, silicon (Si) etc.) as a metal is shown, and a transition metal as metal on the left side of the graph A region (B) which is an elemental composition containing M2 (for example, niobium (Nb), tantalum (Ta) or the like) as a main component is shown. And, it is shown that the gas barrier film has a mixed region. In the case where the gas barrier film has a region (A) and a region (B) described later as shown in the figure, the mixed region is a part of the region (A) and a part of the region (B). It becomes an area shown overlapping with.

  The preferred type of non-transition metal M1 in the mixed region is the same as the preferred non-transition metal M1 in the region (A) described later, and the preferred type of transition metal M2 in the mixed region is preferred in the region (B) described later It is similar to the type of transition metal M2.

  The thickness of the mixed region is not particularly limited, but is preferably 5 nm or more continuously in the thickness direction. The reason for this is that the presence of 5 nm or more continuously in the thickness direction makes the effect of improving the flexibility greater, and the region (a) to be 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 still more 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 still more preferably 30 nm or less from the viewpoint of optical properties.

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

  The mixed region is a compound derived from non transition metal M1 (a compound containing non transition metal M1 alone or a non transition metal M1 alone) and a compound derived from transition metal M2 (a compound containing transition metal M2 alone or transition metal M2) Or a mixture thereof may be contained as a component, or a compound derived from non-transition metal M1 and transition metal M2 may be contained as a component. Moreover, both of these may be contained as a component.

  Here, in the present specification, a mixture of a compound derived from non transition metal M1 and a compound derived from transition metal M2 in the mixed region is derived from a compound derived from non transition metal M1 and transition metal M2. Compounds are mixed with each other without being chemically bonded to each other. Examples of the mixture include those in which niobium oxide and silicon oxide are mixed without being chemically bonded to each other.

  When a mixture of a compound derived from non transition metal M1 and a compound derived from transition metal M2 is contained in the mixed region, the compound derived from preferred non transition metal M1 in the mixture is the region (A) described later. Preferred is the same as the compound derived from non-transition metal M1. Moreover, the compound derived from the preferred transition metal M2 in the mixture is the same as the compound derived from the preferred transition metal M2 in the region (A) described later.

  Moreover, in the present specification, the compound derived from the non-transition metal M1 and the transition metal M2 is such that the compound derived from the non-transition metal M1 and the compound derived from the transition metal M2 mutually chemically bond It represents a formed compound or a compound formed by physical binding due to intermolecular interaction or the like. In the present specification, as a compound derived from non-transition metal M1 and transition metal M2, for example, it has a structure in which a niobium atom and a silicon atom form a chemical bond directly or through an oxygen atom. Compounds etc. may be mentioned.

  In the mixed region, in general, the composition changes continuously or stepwise in the thickness direction of the gas barrier film. Therefore, the mixed region can suppress stress concentration, and the excellent flexibility of the gas barrier film can be realized. In addition, it is preferable that a mixed region changes a composition continuously from a viewpoint of flexibility.

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

  The mixed region is preferably formed in the vicinity of the interface between the region (A) of the gas barrier film and the region (B). At this time, the flexibility improvement effect of the gas barrier film resulting from the composition changing continuously or stepwise becomes larger. That is, the gas barrier film according to a preferred embodiment of the present invention comprises a region (A) containing 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 area (a) represents an area in which M1M2 _x N _y has a specific composition in the above-described mixed area. The gas barrier film of the present invention having such a configuration can have both excellent flexibility and high water vapor barrier properties 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) and the following formula (1) when the composition is represented by M1M2 _x N _y in the atomic composition distribution profile obtained when the XPS composition analysis is performed in the thickness direction. It has a region (a) (hereinafter, also simply referred to as a region (a)) satisfying the following formula (2).

  x is the existing atomic ratio of the transition metal M2 to the non-transition metal M1, y is the existing atomic ratio of the nitrogen to the non-transition metal M1, but the region (a) contains the formula (1) and the formula (2) It is necessary to be satisfied at the same time. That is, at least a region in which the non-transition metal M1 atom and the transition metal M2 atom exist simultaneously, 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) is It has been found out that the condition of 0.2 or more and 3.0 or less is a condition for exhibiting high water vapor barrier properties in a high temperature and high humidity environment. Here, even if the existing 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, non-transition It is considered that the water vapor barrier property in a high temperature and high humidity environment is lowered because the bond between the metal M1 atom and the transition metal M2 atom is reduced. Then, a region in which the non-transition metal M1 atom, the transition metal M2 atom and the nitrogen atom simultaneously exist is formed, 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) Is not less than 0.2 and not more than 3.0, and the existing atomic ratio of nitrogen atom to non-transition metal M1 atom (nitrogen atom / non-transition metal M1 atom) is more than 0.6 and not more than 1.4, It is a condition for developing extremely high water vapor barrier properties in a high temperature and high humidity environment.

  Since the region (a) can impart high water vapor barrier properties in a high temperature and high humidity environment to the gas barrier film, the gas barrier film is a water vapor barrier in a high temperature and high humidity environment at a level required for organic EL elements and the like. While maintaining the properties, it is possible to make a thin film and to have excellent flexibility.

  When the region (a) has a plurality of non-transition metals M1 or a plurality of transition metals M2, x is calculated from the weighted sum of the content of each metal.

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

  Here, the maximum value (y maximum value) of the existing atomic ratio of the nitrogen atom to the non-transition metal M1 atom in the region (a) is expressed by the elemental composition within the range of y above 0.6. Although it is 4 or less, it is preferably 0.65 or more from the viewpoint of obtaining higher water vapor barrier properties in a high temperature and high humidity environment. In addition, the maximum value (y maximum value) of the existing atomic ratio of nitrogen atoms to non-transition metal M1 atoms is preferably 1 or less from the viewpoint of obtaining higher water vapor barrier properties in a high temperature and high humidity environment, It is more preferable that 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 enhancing the water vapor barrier property in a high temperature and high humidity environment, the region (a) preferably exists continuously in the thickness direction at 1 nm or more, and more preferably at 2 nm or more, It is more preferable to exist 3 nm or more, and it is particularly preferable to exist 4 nm or more. And when forming the non-transition metal M1 containing layer and the transition metal M2 containing layer which are mentioned later together by vapor phase film formation, extremely high flexibility and extremely high water vapor barrier property in a high temperature and high humidity environment are further enhanced. From the viewpoint of obtaining stably, it is most preferable that the region (a) be continuously present 5 nm or more 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. In addition, the region (a) is not particularly limited, but preferably 30 nm or less continuously in the thickness direction, and more preferably 15 nm or less, from the viewpoint of obtaining better light transmittance. The presence of 10 nm or less is more preferable, and the presence of 8 nm or less is particularly preferable.

  The control of the composition and thickness of such a region (a) is a method of forming the non-transition metal M1 containing layer and the transition metal M2 containing layer, the forming sequence, the non transition metal M1 containing After forming a layer (or transition metal M2 containing layer), it can carry out by selecting the storage method etc. before forming a transition metal M2 containing layer (or non transition metal M1 containing layer) suitably.

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

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

  The metal element having the largest atomic composition ratio in the thickness direction of the gas barrier film is the two non transition metal M1 and transition metal M2, ie, the atomic composition of the non transition metal M1 among the metal elements. The ratio and the atomic composition ratio of the transition metal M2 may be both maximum and the same. In the present invention, such a region (or point) is treated as being included in the region (A).

  Here, non-transition metal M1, transition metal M2, oxygen (O), nitrogen (N) and carbon (C) in the region (A) from the viewpoint that the water vapor barrier property in a high temperature and high humidity environment is further enhanced. 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 of a) (unit: atm%) (hereinafter also referred to as [M1]) is preferably 20 atm% or more, 22 atm % Or more is more preferable, and 24 atm% or more is more preferable. Further, from the viewpoint of obtaining a 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 more preferably 36 atm% or less.

  Also, as described above, the ratio of the amount of non-transition metal M2 atom to the total amount of [M1] and the non-transition metal M1, transition metal M2, oxygen (O), nitrogen (N) and carbon (C) atoms When there is a region (or a point) having the same value as (unit: atm%) (hereinafter also referred to as [M2]), from the viewpoint of further enhancing the water vapor barrier property in a high temperature and high humidity environment, 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 an atom 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 hydrogen in the region (A) can be measured by Rutherford Backscattering Spectroscopy (RBS), HFS analysis (Hydrogen Forward Scattering Spectrum). However, non-transition metal M1, transition metal M2, oxygen (O), nitrogen (with respect to the total amount of all atoms present in region (A), from the viewpoint that the water vapor barrier property in a high temperature and high humidity environment is further enhanced. 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, 99 atm % Or more is more preferable (upper limit 100 atm%).

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

  The form of the non-transition metal M1 as a 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). The non-transition metal M1 is, for example, contained in the form of an oxide, nitride, carbide, oxynitride or oxycarbide of the non-transition metal M1. Among them, the non-transition metal M1 is preferably contained in the state of a compound containing the non-transition metal M1, and more preferably contained in the state of a compound containing the non-transition metal M1 and nitrogen. The form of the non-transition metal M1 contained in the region (A) may be one kind alone or two or more kinds in combination.

  The region (A) may be a single layer or a stacked structure of two or more layers. When the region (A) has a laminated structure of two or more layers, the non-transition metal compounds contained in the region (A) may be the same or different.

  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. The thickness of the region (A) is not particularly limited, but may be 100 nm or less, may be 50 nm or less, or 30 nm or less according to the presumed mechanism in which the region (A) is formed. Good.

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

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

  Here, the average value in the thickness direction of [M2] in the region (B) is preferably 16 atm% or more, and 18 atm% from the viewpoint that the water vapor barrier property in a high temperature and high humidity environment is further enhanced. The above content is more preferable, and 20 atm% or more is more preferable. Also, 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, and more preferably 38 atm% or less Preferably, it is more preferably 36 atm% or less.

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

  The transition metal (M2) is not particularly limited, and any transition metal may be used alone or in combination. Here, transition metals refer to Group 3 elements to Group 11 elements in the long period periodic table, and as transition metals, 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, Au and the like.

  Among them, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce and the like can be mentioned as the transition metal (M2) from which good water vapor barrier properties can be obtained. Among these, from the various examination results, it is preferable to use Nb, Ta, and V, which are Group 5 elements, particularly from the viewpoint that bonding to the non-transition metal (M1) contained in the gas barrier film tends to occur. 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 (in particular, Nb), and the non-transition metal (M1) described later is Si in detail, a significant improvement in the water vapor barrier properties can be obtained. It is a particularly preferred combination. It is considered that this is because a bond between Si and a Group 5 element (in particular, Nb) is particularly easily generated. Furthermore, from the viewpoint of optical properties, Nb and Ta are particularly preferable as the transition metal (M2) from which a compound having good transparency can be obtained, and Nb is most preferable.

  The form of the transition metal M2 as a component of the region (B) is not particularly limited as long as it is a compound derived from the transition metal M2 (transition metal M2 alone or a compound containing the transition metal M2). The transition metal M2 is, for example, included in the form of an oxide, a nitride, a carbide, an oxynitride, or an oxycarbide of the transition metal M2. Among them, the transition metal M2 is preferably contained in the state of a compound containing the transition metal M2, and more preferably contained in the state of transition metal oxide. The form of the transition metal M2 contained in the region (B) may be one kind alone, or two or more kinds in combination.

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

  The region (B) is considered to form the region (a) by being formed adjacent to the region (A) and to impart high water vapor barrier properties in a high temperature and high humidity environment. (B) The water vapor barrier property is not necessarily required for itself. Thus, region (B) can be effective even with relatively thin layers. Specifically, the thickness of the region (B) is preferably 2 nm or more from the viewpoint of forming the region (a) with a thickness that achieves higher water vapor barrier properties in a high temperature and high humidity environment, The thickness 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 still more preferably 25 nm or less, from the viewpoint of obtaining a better light transmittance. The thickness is particularly preferably 15 nm or less, and particularly preferably 12 nm or less.

[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 a film is formed on an object to be formed (for example, a resin substrate). The region (A) / region (B) may be arranged in order from the object side, or the region (B) / region (A) may be arranged in order from the film formation object side on the film formation object It may be done. However, higher water vapor barrier properties and better flexibility in a high temperature and high humidity environment can be arranged in the order of region (A) / region (B) from the film formation object side on the film formation object. It is preferable from the viewpoint of obtaining. In addition, within the range of the thickness of the gas barrier film from which excellent flexibility can be obtained, the gas barrier film is a unit or region (B) / region (A) consisting of a laminated structure of region (A) / region (B) It may have a structure in which a plurality of units having a laminated structure is laminated, for example, an alternate laminated structure.

<Method of producing gas barrier film>
The method for producing a gas barrier film according to an embodiment of the present invention is not particularly limited, but it is preferable to include forming the non-transition metal M1 containing layer and the transition metal M2 containing layer so as to be in contact with each other.

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

  Also according to the second embodiment of the present invention, in the gas barrier film, means capable of achieving both excellent flexibility and high water vapor barrier property in a high temperature and high humidity environment can be provided. Moreover, according to the method for producing a gas barrier film according to the second aspect of the present invention, the gas barrier film according to the first aspect of the present invention described above can be produced.

  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 is 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, the laminated structure 10 of the gas barrier film formed on the film formation target according to FIG. 2 forms the non-transition metal M1 containing layer 12 on the film formation target 11, and then the transition metal M2 containing layer 13 Form. In addition, the laminated structure 10 ′ of the gas barrier film formed on the film formation target according to FIG. 3 forms the transition metal M2 containing layer 13 on the film formation target 11, and then the non transition metal M1 containing layer 12 Form. In FIG. 2 and FIG. 3, the non-transition metal M1 containing layer 12 and the transition metal M2 containing layer 13 are formed to be in contact with each other. Moreover, the film-forming target 11 is not particularly limited as long as the gas-barrier film can be formed thereon. For example, when producing a gas barrier film, the film formation target object 11 may 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 formed after the formation of the non-transition metal M1 containing layer 12 (or the transition metal M2 containing layer 13). As a result of the transition metal M1 containing layer entering the non transition metal M1 containing layer 12 or the material containing the non transition metal M1 entering the transition metal M2 containing layer 13 when forming the transition metal M1 containing layer 12) It is believed to be formed. In addition, the mixed region including the region (A), the region (B) and the region (a) causes spontaneous diffusion of substances between these layers after forming the non-transition metal M1 containing layer and the transition metal M2 containing layer It is believed to be formed as a result.

  Here, the control of the composition and thickness of the region (a) is a method of forming the non-transition metal M1 containing layer and the transition metal M2 containing layer, the formation order, the non transition metal M1 containing layer (or the transition metal M2 containing layer) It can carry out by the storage method etc. before forming a transition metal M2 containing layer (or non transition metal M1 containing layer), etc. after formation.

  In the method for producing a gas barrier film according to one embodiment of the present invention, the order of forming the non-transition metal M1 containing layer and the transition metal M2 containing layer is not particularly limited, and a film forming target (for example, resin base material etc.) ) May be formed in the order of non-transition metal M1 containing layer / transition metal M2 containing layer from the film forming object side, or on the film forming object from the film forming object side, containing transition metal M2 The layer / non-transition metal M1 containing layer may be formed in this order. However, forming a 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 higher water vapor barrier properties in a high temperature and high humidity environment and is better It is preferable from the viewpoint of obtaining flexibility. The reason is that the formation of the region (a) is easier and the thickness of the region (a) can be further increased. In addition, within the range of the thickness of the gas barrier film from which excellent flexibility can be obtained, the method for producing the gas barrier film is a unit consisting of a non-transition metal M1 containing layer / transition metal M2 containing layer or a transition metal M2 containing layer / It may be a method of repeatedly forming a unit composed of the non-transition metal M1 containing layer to form a laminated structure, for example, a method of forming an alternate laminated structure.

  The gas barrier film produced by the method for producing a gas barrier film according to an embodiment of the present invention is the same as the gas barrier film according to an embodiment of the present invention described above.

[Formation of non-transition metal M1 containing layer]
It does not restrict | limit especially as a method to form a non-transition metal M1 containing layer, For example, the vapor phase film-forming method and the apply | coating method are mentioned. Among them, the non-transition metal M1 containing layer and the transition metal M2 containing layer can be continuously formed while transporting the film formation target, and from the viewpoint of excellent productivity, it is a vapor deposition method. Is preferred. Here, as a method of forming each layer while transporting the film formation target, for example, a roll-to-roll method may be mentioned. That is, a manufacturing method according to a preferred embodiment of the present invention is a manufacturing method including forming a non-transition metal M1 containing layer by a vapor phase film forming method.

  In one embodiment of the present invention, the raw material for forming the non-transition metal M1 containing layer is particularly limited if it is a compound derived from non-transition metal M1 (non-transition metal M1 alone or a compound containing non-transition metal M1) I will not. Moreover, as a raw material for forming a non-transition metal M1 containing layer, the substance (a metal single-piece | unit, the compound containing a metal) originating in another metal may further be included. At this time, 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 transition metal M2 (transition metal M2 alone, compound containing transition metal M2) It may be done. In this case, the classification of layers 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 determined by the XPS analysis method in the same manner as the atomic composition profile of the gas barrier film described above. Measure. Then, among the metal elements contained in the constituent components of the produced layer, a layer in which the content of the non-transition metal M1 is the largest as the atomic composition ratio is treated as the formation of the non-transition metal M1 containing layer.

(Gas vapor deposition method)
The vapor deposition method is not particularly limited. For example, physical vapor deposition (PVD) such as sputtering, evaporation, ion plating, etc., chemical vapor deposition (CVD), ALD Chemical vapor deposition methods such as (Atomic Layer Deposition) may be mentioned. Among them, physical vapor deposition is preferable, sputtering or CVD is more preferable, and sputtering is more preferable, because film formation can be performed without damaging the object to be formed, and high productivity can be obtained.

  The film formation setting thickness (the total thickness in the case of a laminated structure of two or more layers) when forming the layer containing the non-transition metal M1 by the vapor phase film formation method is 10 nm or more from the viewpoint of water vapor barrier properties. Is preferably 30 nm or more. Further, the film formation setting thickness at the time of forming the layer containing the non-transition metal M1 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.

  In the non-transition metal M1 containing layer, the thickness direction of the atomic ratio (N / M1) of the nitrogen atom to the non-transition metal M1 atom calculated from the result of the atomic composition distribution profile obtained when performing the XPS composition analysis The average value of is preferably 0.10 or more, particularly preferably 0.50 or more, and most preferably 0.90 or more. If the average value in the thickness direction of the 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. In addition, in the formation of the transition metal M2 containing layer, for example, the transition metal M2 containing layer is formed by using a nitride or an oxynitride of the transition metal M2 as a raw material, introducing nitrogen during film formation, or the like. Region (a) is more likely to be formed in the mixed region. Under the present circumstances, when forming the layer containing nitrogen as a transition metal M2 containing layer, the average value of the thickness direction of the existing atomic ratio (N / M1) of the nitrogen atom to the non transition metal M1 atom is 0.50 or more Is preferred. The reason for this is that the region (a) can be formed better in 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 (N / M1) of nitrogen atoms to non transition metal M1 atoms is 0. It is more preferably 60 or more, still more preferably 0.80 or more, particularly preferably 0.85 or more, and most preferably 0.90 or more. The average value in the thickness direction of the existing atomic ratio (N / M1) of the nitrogen atom to the non-transition metal M1 atom is preferably 1.4 or less. The XPS measurement analysis and the atomic composition distribution profile referred to here are the same as those described in the explanation of the atomic composition profile.

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

<< CVD >>
The chemical vapor deposition (CVD) method is a raw material gas containing the component of the target thin film on the material forming the non-transition metal M1 containing layer of the object to be film-formed (for example, resin base material etc.) And a film is deposited by a chemical reaction on the surface of the material forming the non-transition metal M1 containing layer or in the gas phase. In addition, there is a method of generating plasma etc. for the purpose of activating chemical reaction, and known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method Law etc. are mentioned. Although these methods are not particularly limited, 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 the chemical vapor deposition method is advantageous in view of the water vapor barrier property in a high temperature and high humidity environment. In addition, when a layer containing the non-transition metal M1 is formed by vacuum plasma CVD, plasma CVD under atmospheric pressure or a pressure near atmospheric pressure, metal compounds as raw materials (also referred to as raw materials), decomposition gas, decomposition temperature, By selecting conditions such as input power, it is preferable because a non-transition metal M1 containing layer having a target composition can be formed.

  Here, as plasma CVD, CCP (Capacitively Coupled Plasma)-CVD, ICP (Inductively Coupled Plasma Inductively Coupled Plasma)-CVD, microwave CVD, ECR (Electron Cyclotron Resonance)-CVD, atmospheric pressure barrier discharge CVD Various plasma CVDs, such as, are suitably utilized.

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

  The source gas used in the plasma CVD method is not particularly limited, and when the non-transition metal M1 is silicon, silane gas, disilane gas, TEOS (tetraethoxysilane), HMDSO (hexamethyldisiloxane), HMDSN (hexamethyldisilane). Silazane), TMS (tetramethylsilane), hydrazine gas, ammonia gas, nitrogen gas, hydrogen gas, argon gas, neon gas, helium gas, etc., source gases used for forming a silicon-containing film by a known plasma CVD method May be selected and used as appropriate. A preferable example of the source gas is a combination of silane gas, ammonia gas, and hydrogen gas. Here, from the viewpoint of further enhancing the water vapor barrier property in a high temperature and high humidity environment, the source gas preferably contains nitrogen gas. One preferable example of the source gas is 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 still more preferably 200 to 700 sccm. Further, the ratio of the flow rate of nitrogen gas to the flow rate of the source gas is preferably 0 to 70%, and more preferably 30 to 60%.

  In addition, the film formation conditions may also be set as appropriate in accordance with the source gas to be used, the thickness of the layer to be formed, and the like. At the time of film formation, the supply amount of reaction gas, supply balance of each reaction gas, film formation pressure, plasma excitation power, plasma excitation frequency, application power such as bias, film formation target (eg, substrate etc.) temperature, film formation The composition of the gas barrier film can be controlled by controlling the non-transition metal M1 containing layer by appropriately controlling the pre-attainment pressure, the distance between the film formation target and the plasma generation region, and the like. For example, the distance between electrodes is preferably 10 to 40 mm. For example, the deposition pressure of the chamber is preferably 1 to 100 Pa. And, for example, the plasma excitation power is preferably 100 to 2000 W.

  The vacuum plasma CVD method, which is a preferred embodiment of the CVD method, will be specifically described below with reference to FIG. FIG. 4 is a schematic view showing an example of a vacuum plasma CVD apparatus that can be used to form the non-transition metal M1 containing layer.

  In FIG. 4, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom side inside the vacuum chamber 102. Further, on the ceiling side inside the vacuum chamber 102, a cathode electrode 103 is disposed at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum evacuation 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 and cooling device 160 having a storage device is provided.

  The heating and cooling device 160 is configured to measure the temperature of the heat medium, heat or cool the heat medium to the stored set temperature, and supply the heat medium to the susceptor 105. The supplied heat medium flows inside the susceptor 105 to heat or cool the susceptor 105 and return 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 it to the susceptor 105. In this way, the cooling medium circulates between the susceptor and the heating and cooling device 160, and the susceptor 105 is heated or cooled by the supplied heating medium of the set temperature.

  The vacuum chamber 102 is connected to a vacuum evacuation system 107. Before the film forming 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 to start from room temperature. The temperature is raised to the set temperature, and the heat medium of the set temperature is supplied to the susceptor 105. The susceptor 105 is at room temperature at the start of use, and when the heat medium at the set temperature is supplied, the susceptor 105 is heated.

  After circulating a heat medium having a set temperature for a certain period of time, a film formation target (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. 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 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 the CVD gas is supplied from the gas introduction system 108 into the vacuum chamber 102 and the heating medium with a constant temperature is supplied from the heating and cooling device 160 to the susceptor 105, the high frequency power supply 109 is started and a high frequency voltage is applied to the cathode electrode 103, A plasma of the introduced CVD gas is formed. When the CVD gas activated in the plasma reaches the surface of the film formation object 110 on the susceptor 105, a thin film which is a non-transition metal M1 containing layer grows on the surface of the film formation object 110. The distance between the susceptor 105 and the cathode electrode 103 at this time is appropriately set.

  Further, the flow rates of the source gas and the decomposition gas are appropriately set in consideration of the source gas, the type of the decomposition gas, 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 thin film growth, a heating medium having a constant temperature is supplied from the heating and 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 in a state of being maintained at a constant temperature. In general, the lower limit temperature of the growth temperature when forming the 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 object 110. The lower limit temperature and the upper limit temperature vary depending on the material of the thin film to be formed and the material of the thin film already formed, but the preferred lower limit temperature for securing a film having high water vapor barrier properties is 50 ° C. or higher. It is preferable that it is below the heat-resistant temperature of the film-forming object.

  The correlation between the film quality of the thin film formed by the vacuum plasma CVD method and the film forming temperature, and the correlation between the damage to the film forming object 110 and the film forming temperature is determined in advance, and the lower limit temperature and the upper limit temperature are determined. . For example, it is preferable that the temperature of the film-forming object 110 in a vacuum plasma CVD process is 50-250 degreeC.

  Furthermore, the relationship between the temperature of the heat medium supplied to the susceptor 105 and the temperature of the film-forming target 110 is previously measured when a plasma is formed by applying a high frequency voltage of 13.56 MHz or more to the cathode electrode 103. In order to maintain the temperature of the film formation object 110 at or above the lower limit temperature and below the upper limit temperature during the vacuum plasma CVD process, the temperature of the heat medium supplied to the susceptor 105 is determined. For example, the lower limit temperature (preferably 50 ° C.) is stored, and a heat medium 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 returned from the susceptor 105 is heated or cooled, and the heat medium having a set temperature (preferably, 50 ° C. or more) is supplied to the susceptor 105. Here, for example, a mixed gas of a silane gas, an ammonia gas and a nitrogen gas is supplied as a CVD gas, and the film forming object 110 is maintained at a temperature condition of the lower limit temperature or more and the upper limit temperature or less. A silicon (SiN) film is formed.

  Immediately after 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 and cooling device 160 is lower than the set temperature. Therefore, immediately after the start-up, the heating and cooling device 160 heats the heated heat medium to be heated to the set temperature, and supplies the heat medium 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 from the lower limit temperature to the upper limit temperature.

  When thin films are continuously formed on a plurality of film formation objects 110, the temperature of the susceptor 105 is increased by the heat flowing from the plasma. In this case, since the heat medium returned from the susceptor 105 to the heating and cooling device 160 has a temperature higher than the lower limit temperature (preferably 50 ° C.), the heating and cooling device 160 cools the heat medium and the heat medium at the set temperature Is supplied to the susceptor 105. Thereby, the thin film can be formed while maintaining the film formation target object 110 in the range of the lower limit temperature or more and the upper limit temperature or less. As described above, the heating and cooling device 160 heats the heat medium when the temperature of the heat medium returned is lower than the set temperature, and cools the heat medium when the temperature is higher than the set temperature. Also, the heat medium having the set temperature is supplied to the susceptor, and as a result, the temperature of the film formation target 110 is maintained in the temperature range from the lower limit temperature to the upper limit temperature. When the thin film is formed to a predetermined film thickness, the film formation object 110 is carried out of the vacuum chamber 102, and the non-film formation film formation object 110 is carried into the vacuum chamber 102. A thin film is formed while supplying a heat medium.

«Sputter»
Deposition by sputtering is advantageous in that the deposition rate is higher and productivity is higher. In addition, it is extremely high to form both the non-transition metal M1 containing layer and the transition metal M2 containing layer by sputtering, and in particular, to continuously form each layer by sputtering while transporting the film formation target. There is an advantage of having productivity.

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

  The type of non-transition metal M1 contained in the target and the preferred type of non-transition metal M1 are the same as the non-transition metal M1 described for the region (A). Further, as the target containing the non-transition metal M1, the same one 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 containing the non-transition metal M1, a commercially available silicon target can be mentioned. Moreover, as a target containing the said non-transition metal M1, it describes, for example in Unexamined-Japanese-Patent 2000-026961, Unexamined-Japanese-Patent 2009-215651, Unexamined-Japanese-Patent 2003-160862, 2012-007218 etc. It is possible to use a target containing a plurality of elements.

(Coating method)
The non-transition metal M1 containing layer may be formed by a coating method. A non-transition metal M1 containing 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 application method is a layer with few defects because there is no contamination such as particles at the time of film formation. The non-transition metal M1 containing layer may be a single layer or a laminated structure of two or more layers.

  In the non-transition metal M1 containing layer formed by the coating method, the atomic ratio of the nitrogen atom to the non-transition metal M1 atom, which is calculated from the result of the atomic composition distribution profile obtained when performing the XPS composition analysis (N / The maximum value in the thickness direction in a region within 30 nm from the surface layer side (surface side on the 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, 0 It is very preferable that it is .90 or more. Region (a) in the mixed region that the maximum 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 side is 0.90 or more Is more likely to be formed. In addition, in the formation of the transition metal M2 containing layer, for example, the transition metal M2 containing layer is formed by using a nitride or an oxynitride of the transition metal M2 as a raw material, introducing nitrogen during film formation, or the like. Region (a) is more likely to be formed in the mixed region. At this time, when forming a layer containing nitrogen as the transition metal M2 containing layer, the atomic ratio of nitrogen atoms to non transition metal M1 atoms in the region within 30 nm from the surface side of the non transition metal M1 containing layer (N / The maximum value in the thickness direction of M1) is preferably 0.50 or more. The reason for this is that the region (a) can be formed better in 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 non transition metal M1 atoms in the region within 30 nm from the surface side of the non transition metal M1 containing layer The maximum value in the thickness direction of N / M1) is more preferably 0.60 or more, and most preferably 0.90 or more. In addition, the maximum value in the thickness direction of the existing atomic ratio (N / M1) of nitrogen atoms to non-transition metal M1 atoms in the region within 30 nm from the surface 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 side of the non-transition metal M1 containing layer is defined is that the distribution method is large in the thickness direction. This is because the formation of the region (a) is greatly affected. The XPS measurement analysis and the atomic composition distribution profile referred to here are the same as those described in the explanation of the atomic composition profile.

  Although the case where non-transition metal M1 is silicon (Si) is demonstrated to an example below, the present invention is not limited to this.

«Silicon containing compounds»
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, polysiloxane, polysilane, polycarbosilane and the like. In addition, a well-known compound can be used as polysiloxane, polysilsesquioxane, polysilazane, polysiloxan, 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 examples of the silicon-containing compound include a polysilazane having a silicon-nitrogen bond and a silicon-hydrogen bond, a polysiloxane having a silicon-nitrogen bond, a polysiloxane having a silicon-hydrogen bond, and a silicon-hydrogen bond. Polysilsesquioxane and polysilane having a silicon-silicon bond can be preferably used. The silicon-containing compounds may 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 a ceramic such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _z N _y having a bond such as Si-N, Si-H, or N-H. It is a precursor inorganic polymer. The polysilazane is not particularly limited and any known one may be used, but it is more preferable to have a structure of the following general formula (I).

In the general formula (I), each of R ₁ , R ₂ and R ₃ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group Is preferred. At this time, R ₁ , R ₂ and R ₃ may be the same or different. In addition, n is an integer, and it is preferable that polysilazane having a structure represented by General Formula (I) is defined to have 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, perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable in the compound having a structure represented by the general formula (I). Perhydropolysilazane is presumed to have a linear structure and a ring structure centering on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (in terms of polystyrene) in number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

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

  The polysilazane may be a commercially available product. The commercially available product is generally in the form of a solution dissolved in an organic solvent, and in this case, the commercially available product can be used as it is as a coating liquid for forming the layer (B). Commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. 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 described later can be 100 mass% when the total mass of the non-transition metal M1 containing layer before the modification treatment is 100 mass%. In addition, when the silicon-containing layer before the modification treatment contains 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 10% by mass or more 99.5 mass% or less is more preferable, 10 mass% or more and 99 mass% or less is more preferable, 40 mass% or more and 98 mass% or less is more preferable, and 70 mass% or more and 97 mass% % Is particularly preferable, 90% by mass or more and 97% by mass or less is extremely preferable, and 93% by mass or more and 97% by mass or less is most preferable.

<< coating solution for forming silicon-containing layer >>
The coating liquid for forming a silicon-containing layer is a liquid containing the silicon-containing compound as an essential component. The coating liquid 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 contain water and reactive groups (eg, hydroxyl group or amine group) which easily react with the silicon-containing compound, but silicon An organic solvent inert to the contained compound is preferable, and an aprotic organic solvent is more preferable. Specifically, as the solvent, an aprotic solvent; for example, hydrocarbon such as aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon and the like such as pentane, hexane, cyclohexane, toluene, xylene, Solvesso, and terpene 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 etc. Ethers of the following: for example, tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes) and the like can be mentioned. The solvent is selected according to the purpose 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 It is 50% by mass, more preferably 2 to 40% by mass.

  When reforming the silicon-containing layer, the coating liquid for forming a silicon-containing layer preferably contains a catalyst in order to accelerate the reforming. As a catalyst, a basic catalyst is preferable, 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, Pd compounds such as Pd propionate And metal catalysts such as Rh compounds such as Rh acetylacetonate and N-heterocyclic compounds. Among 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, and more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the amount of catalyst added in this range, excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects and the like can be avoided.

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

«Coating method»
As a method of applying the coating solution for forming a silicon-containing layer, a conventionally known appropriate wet coating method may be employed. Specific examples include spin coating method, roll coating method, flow coating method, inkjet 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. Be

  The coating thickness may be appropriately set according to the desired thickness and purpose.

  After applying the coating solution, the coating is dried. By drying the coating, organic solvents that may be contained in the coating can be removed. At this time, the organic solvent contained in the coating film may be all dried, but 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.

  It is preferable that the drying temperature of a coating film is 50-200 degreeC. For example, when using a gas barrier film in the form of a gas barrier film and using a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C., the drying temperature is the deformation of the resin substrate due to heat. Preferably, the temperature is set to 150 ° C. or less in consideration of the above. The temperature may be set by using a hot plate, an oven, a 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 to 30 minutes or less. At this time, the lower limit of the drying time is not particularly limited as long as achieving the target drying state is possible, but for example, preferably 30 seconds or more. Further, the drying atmosphere may be any conditions such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, and a reduced pressure atmosphere in which the oxygen concentration is controlled.

  The coating film obtained by applying the coating solution for forming a silicon-containing layer may include a step of removing moisture before or during irradiation with vacuum ultraviolet light. Since the humidity in a low humidity environment changes with temperature, the relationship between temperature and humidity is preferably indicated by the definition of dew point temperature. The dew point temperature is preferably 4 ° C. or less (temperature 25 ° C./relative humidity 25% RH), and the maintained time is preferably 1 minute or more. Although the lower limit of the dew point temperature is not particularly limited, it is usually −50 ° C. or higher.

«Reforming (conversion)»
The coating film containing the silicon-containing compound (coating liquid for forming a silicon-containing layer) can be used as it is as a silicon-containing layer, but the obtained coating film is reformed to convert it to silicon oxynitride or the like. To form a silicon-containing layer. 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 an 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 is further suppressed between the formation of the silicon-containing layer and the formation of the transition metal M2-containing layer.

  Vacuum ultraviolet irradiation is compatible with both batch processing and continuous processing, and can be selected appropriately. For example, in the case of batch processing, it can be processed in an ultraviolet baking furnace equipped with an ultraviolet light source. The ultraviolet baking furnace itself is generally known, and for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd. can be used. Further, when the object is in the form of a long film, it can be made to be ceramic by continuously irradiating ultraviolet rays in a drying zone equipped with the above-mentioned ultraviolet generation source while conveying it. The time required for the ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, depending on the composition and concentration of the silicon-containing layer and the kind of the film formation target.

  The modification by vacuum ultraviolet irradiation uses an optical energy of 100 to 200 nm, preferably an optical energy of 100 to 180 nm, which is larger than the interatomic bonding force in the silicon-containing compound (particularly, 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 advancing an oxidation reaction with active oxygen or ozone while directly cutting it by the action of only photons called photon process. It is. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together.

  The vacuum ultraviolet light 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 a bright 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 them, the Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light of 172 nm having a short wavelength at a single wavelength. Since this light has a large absorption coefficient of oxygen, it can generate radical oxygen atom species and ozone at high concentration with a small amount of oxygen.

  In addition, it is known that the energy of 172 nm light having a short wavelength has a high ability to dissociate the binding of an organic substance. The high energy possessed by the active oxygen and ozone and the ultraviolet radiation enables the coating to be reformed in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power input. In addition, since light having a long wavelength causing temperature rise due to light is not emitted, energy is irradiated in the ultraviolet region, that is, at a short wavelength, so that the rise of the surface temperature of the object to be irradiated is suppressed. Therefore, it is suitable for flexible film materials such as PET which are considered to be susceptible to heat.

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

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

  It is preferable to set it as dry inert gas as gas which satisfy | fills irradiation atmosphere used at the time of vacuum ultraviolet irradiation, and it is more preferable to set it as dry nitrogen gas especially from a viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation storage and changing the flow ratio.

In vacuum ultraviolet irradiation step, preferably the intensity of the vacuum ultraviolet rays in the coated surface of the coating film is subjected is a ^{1mW / cm 2 ~10W / cm 2} , more preferable to be ^{30mW / cm 2 ~200mW / cm 2} , further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, the modification efficiency is improved, and if it is 10 W / cm ² or less, it is possible to reduce the abrasion which may occur on the coating film and the damage to the film forming object.

Irradiation energy amount of the VUV at the surface of the coating film (dose) is preferably 0.1~10J / cm ^2, more preferably 0.1~7J / cm ^2. Within this range, it is possible to suppress the occurrence of cracks due to excessive reforming and thermal deformation of the film formation target, and the productivity is improved.

  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, and more preferably 30 to 300 nm. preferable.

  In the case of forming a non-transition metal M1 containing layer by a coating method, for example, film formation raw material species (polysilazane species etc.) containing the non-transition metal (M1), catalyst species, catalyst content, coating film thickness, 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, reforming method, and reforming conditions.

[Method for forming transition metal M2 containing layer]
It does not restrict | limit especially as a method to form a transition metal M2 containing layer, A vapor phase film-forming method and the apply | coating method are mentioned. Among them, the non-transition metal M1 containing layer and the transition metal M2 containing layer can be continuously formed while transporting the film formation target, and from the viewpoint of excellent productivity, it is a vapor deposition method. Is preferred. Here, as a method of forming each layer while transporting the film formation target, for example, a roll-to-roll method may be mentioned. That is, a manufacturing method according to a preferable embodiment of the present invention is a manufacturing method including forming the transition metal M2 containing layer by a vapor phase film forming 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 transition metal M2 (transition metal M2 alone or a compound containing transition metal M2). Moreover, as a raw material for forming a transition metal M2 containing layer, the substance (a metal single-piece | unit, the compound containing a metal) originating in another metal may further be included. At this time, among the raw materials of the transition metal M2 containing layer, a raw material capable of forming the non-transition metal M1 containing layer, ie, a substance derived from the non transition metal M1 (non transition metal M1 alone, compound containing non transition metal M1) May be further included. In this case, the classification of layers is determined as follows. First, only the transition metal M 2 -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 M2 are determined by the XPS analysis method in the same manner as the atomic composition profile of the gas barrier film described above. Measure. Then, among the metal elements contained in the constituent components of the produced layer, a layer in which the content of the transition metal M2 is the largest as the atomic composition ratio is treated as the formation of the transition metal M2 containing layer.

(Gas vapor deposition method)
The vapor deposition method is not particularly limited. For example, physical vapor deposition (PVD) such as sputtering, evaporation, ion plating, etc., chemical vapor deposition (CVD), ALD Chemical vapor deposition methods such as (Atomic Layer Deposition) may be mentioned. Among them, physical vapor deposition is preferable, sputtering or CVD is more preferable, and sputtering is more preferable, because film formation can be performed without damaging the object to be formed, and high productivity can be obtained.

  Deposition by sputtering is advantageous in that the deposition rate is higher and productivity is higher. In addition, it is extremely high to form both the non-transition metal M1 containing layer and the transition metal M2 containing layer by sputtering, and in particular, to continuously form each layer by sputtering while transporting the film formation target. There is an advantage of having productivity.

  For film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency range, 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 [Formation of Non-Transition Metal M1-Containing Layer], except for the contents specifically described below, and therefore the description thereof is omitted here.

  The type of transition metal M2 contained in the target used in the sputtering method and the type of preferable transition metal M2 are the same as those of the transition metal M2 described for the region (B). Further, as the target containing the transition metal M2, the same one 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 the oxide of the transition metal M2 from the viewpoint of higher deposition rate and higher productivity, and in a high temperature and high humidity environment It is more preferable that it is an oxide of the oxygen deficient transition metal M2 from the viewpoint of further improving the water vapor barrier property of 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 mentioned.

  Here, when forming the oxide film of the transition metal M2 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 a process gas. The ratio of oxygen partial pressure to pressure is preferably 0 to 40%, and more preferably 5 to 30%.

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

  When forming a transition metal M2 containing layer by a vapor phase film-forming method, it is preferable to perform film-forming in the 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. And when the transition metal M2 containing layer contains nitrogen, the substance at the time of spontaneous diffusion of the substance at the interface between the non-transition metal M1 containing layer and the transition metal M2 containing layer, or when forming the transition metal M2 containing layer By entering the non-transition metal M1 containing layer, nitrogen is likely to be introduced into the region near the interface. And 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 producing a gas barrier film according to a preferred embodiment of the present invention is a production method in which the atmosphere of the vapor deposition method is an atmosphere containing nitrogen. The method for introducing nitrogen is not particularly limited. For example, when a nitride film of transition metal M2 is formed as a transition metal M2 containing layer by sputtering, for example, an inert gas and a nitrogen gas may be used as a process gas. 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%, more preferably 20 to 80%.

  The film formation setting thickness at the time of forming the transition metal M2 containing layer is 3 nm or more from the viewpoint of forming a region (a) having a sufficient thickness and obtaining higher water vapor barrier properties in a high temperature and high humidity environment Is preferably, and more preferably 5 nm or more. Moreover, even if the thickness is further increased, the thickness of the region (a) saturates, so from the viewpoint of obtaining a high water vapor barrier property in a high temperature and high humidity environment with a thinner film thickness, and a more excellent flexibility. From the viewpoint of obtaining, it is preferably 30 nm or less, more preferably 20 nm or less, and still more 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 to further include the transition metal M2 and the non-transition metal M1, respectively. Therefore, when forming a non-transition metal M1 containing layer or a transition metal M2 containing layer by a vapor phase film-forming method, a mixing area | region may be directly formed by using a well-known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferably mentioned. The co-sputtering method uses, for example, a single target using a composite target made of an alloy containing both non-transition metal M1 and transition metal M2 or a composite target made of a composite oxide of non-transition metal M1 and transition metal M2 as a sputtering target. It may be spatter. The co-sputtering method may be, for example, multiple simultaneous sputtering using a plurality of sputtering targets containing a single substance of non-transition metal M1 or an oxide thereof and a single substance of transition metal M2 or an oxide thereof. About the method of producing these sputtering targets, and the method of producing the thin film which consists of complex oxides using these sputtering targets, Unexamined-Japanese-Patent 2000-160331, 2004-068109, Unexamined-Japanese-Patent No. The description of the publication 2013-047361 etc. may be referred to suitably. In addition, when the mixed region is formed by the 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 exhibited better is the composition of the mixed region (a), the non transition element M1 in the mixed region (a), the transition element M2 and the nitrogen atom, although the details are unknown. It is presumed that the existence state etc. of is likely to be a more suitable state for the effect of the present invention.

<Gas barrier film and method for producing gas barrier film>
Another embodiment of the present invention is a gas barrier film having a 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 film formation target as a resin substrate and using the method for producing a gas barrier film according to the second embodiment of the present invention.

  In the gas barrier film according to an embodiment of the present invention, the resin substrate surface on which the gas barrier film is formed is not particularly limited, and may be single-sided or double-sided. 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 sides, the region (A) and the region (B) constituting the gas barrier film The lamination number and the lamination order may be the same or different on one side and the other side of the resin substrate.

[Resin base material]
As a resin base material used for the gas barrier film concerning one form of the present invention, a film or sheet which consists of resin is mentioned, and it is preferred that it is a film or sheet which consists of colorless and transparent resin. Examples of resins used for such resin base materials include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclopolyolefins; Polyamide resins; polycarbonate resins; polystyrene resins; polyvinyl alcohol resins; saponified ethylene-vinyl acetate copolymers; polyacrylonitrile resins; acetal resins; polyimide resins; and cellulose ester resins.

  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. Further preferred is polyethylene terephthalate (PET). Moreover, these resins 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 may be a different type of resin.

  The thickness of the resin substrate can be appropriately set in consideration of the stability when producing the gas barrier film of the present invention. The thickness of the resin substrate (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 transported even in a vacuum.

  Furthermore, in the case of forming the gas barrier film according to one embodiment of the present invention using plasma CVD, a thin film is formed while discharging through the resin substrate, so that the thickness of the resin substrate (two or more layers 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.

  Moreover, it is preferable to perform the surface activation process for wash | cleaning the surface of a resin base material to a resin base material from an adhesive viewpoint with the gas barrier film mentioned 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.

[Layer having various functions]
In the gas barrier film according to an 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 substrate on the side of forming the gas barrier film according to an embodiment of the present invention for the purpose of improving the adhesion between the resin substrate and the gas barrier film.

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

A conventionally known additive can also be added to these anchor coating agents. Then, the above-mentioned anchor coating agent is coated on a support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating and the like, and the anchor coating is carried out by drying and removing the solvent, diluent and the like. be able to. As a coating amount of said anchor coating agent, about 0.1-5.0 g / m < ² > (dry state) grade is preferable.

  The anchor coat layer can also 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, the gas generated from the resin base material side is to some extent The 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 preferably about 0.5 to 10 μm.

«Hard coat layer»
The surface (one side or both sides) of the resin substrate may have a hard coat layer. As an example of the material contained in a hard-coat layer, although thermosetting resin and active energy ray curable resin are mentioned, for example, since shaping | molding is easy, active energy ray curable resin is preferable. Such curable resins can be used alone or in combination of two or more.

  The active energy ray curable resin is a resin which is cured through a crosslinking reaction or the like by irradiation of active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated bond is preferably used, and the active energy ray curable resin is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. The hard coat layer is formed. As the active energy ray curable resin, an ultraviolet curable resin, an electron beam curable resin and the like can be mentioned as a typical one, but an ultraviolet curable resin which is cured by ultraviolet irradiation is preferable. As the ultraviolet curable resin, for example, 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 a polyfunctional (meth) acrylate monomer such as meta) acrylate, polyester (meth) acrylate, melamine (meth) acrylate, polyether (meth) acrylate, polyethylene glycol (meth) acrylate and glycerol (meth) acrylate And resin compositions 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, Z731L by Aika Industrial Co., Ltd. and OPSTAR (op star) (registered trademark) Z7527 by JSR Corporation 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 spin coating method, spray method, blade coating method, dip method, or dry coating method such as vapor deposition method. Is preferred.

  Although the drying temperature in particular of the coating film at the time of forming a hard-coat layer is not restrict | limited, It is preferable that it is 40-120 degreeC.

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

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

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

«Smooth layer»
The gas barrier film according to an embodiment of the present invention may have a smooth layer between the resin substrate and the gas barrier film. The smooth layer used in one embodiment of the present invention flattens the rough surface of the resin base on which protrusions and the like are present, or fills the unevenness and pinholes generated in the transparent inorganic compound layer by the projections present on the resin base. Provided to flatten the surface. 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. As a UV curable resin composition, for example, 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, urethane A resin composition comprising a polyfunctional acrylate monomer such as (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyethylene glycol (meth) acrylate, glycerol (meth) acrylate, amorphous fluorine-containing polymer The resin composition etc. which contain are mentioned. 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 can be used as the commercially available product. Examples of OPSTAR (registered trademark) series manufactured by JSR Corporation include OPSTAR (opstar) (registered trademark) Z7527 and the like. In addition, it is possible to use any mixture of the above resin compositions, and it is possible to use a photosensitive material containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule. There is no particular limitation.

  Specifically, as a thermosetting material, Tuttoprom series (organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat Co., Ltd., nano hybrid silicone manufactured by Adeka Co., Ltd., Unidic manufactured by DIC Co., Ltd. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (super 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. A coat, a thermosetting urethane resin consisting of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicone resin and the like can be mentioned. Among these, it is particularly preferable to use an epoxy resin-based material having heat resistance.

  The method for forming the smooth layer is not particularly limited, but it may be formed by a wet coating method (coating method) such as spin coating method, spray method, blade coating method, dip method or dry coating method such as vapor deposition method. preferable.

  The conditions for drying the smooth layer and the conditions for light irradiation when the material forming the smooth layer is a photosensitive material may be the same as the conditions for the hard coat layer described above.

  In formation of a smooth layer, additives, such as an antioxidant, a ultraviolet absorber, and a plasticizer, can be added to the above-mentioned photosensitive resin as needed. Further, regardless of the lamination position of the smooth layer, an appropriate resin or additive may be used in any smooth layer for the purpose of improving film formability and preventing the occurrence 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 the balance adjustment of the optical properties of the film.

  The smoothness of the smooth layer is a value represented by the surface roughness defined by JIS B 0601: 2001, and the ten-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 by the application method, the application property such as a wire bar or a wireless bar is applicable even when the application means contacts the smooth layer surface. It is less likely to be damaged, and it is easy to smooth the unevenness after application.

<Electronic Device and Method of Manufacturing Electronic Device>
The gas barrier film according to an embodiment of the present invention and the gas barrier film according to an embodiment of the present invention are degraded in performance by chemical components in the air (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.) It is preferably applicable to the device. Thus, another aspect of the present invention is an electronic device including the gas barrier film according to an aspect of the present invention or the gas barrier film according to an aspect of the present invention.

  Moreover, the further another one form of this invention seals the functional layer surface of an electronic device by the sealing member containing the gas barrier film which concerns on one form of this invention, or the gas barrier film which concerns on one form of this invention A method of manufacturing an electronic device.

  The sealing member containing a gas barrier film may be a single gas barrier film. In this case, the gas barrier film is formed directly on the functional layer surface of the electronic device to seal the functional layer surface of the electronic device. It may be included. 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. The sealing resin layer is not particularly limited, and examples thereof include a thermosetting sheet-like adhesive (epoxy resin) and the like. Here, the following method is 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-formed surface of the sealing member containing the gas barrier film or the gas barrier film and the functional layer surface of the electronic device are continuously superposed. Next, the laminate of the sealing member and the electronic device is disposed in the decompression device, and the stacked base material and the sealing member are pressed and held under high temperature decompression conditions. Subsequently, the sample is returned to the atmospheric pressure environment, and the adhesive is further cured by heating for a certain time in a high temperature environment.

  As an electronic device, an organic electroluminescent element (organic EL element), a liquid crystal display element (LCD), a thin-film transistor, a touch panel, electronic paper, a solar cell (PV) etc. can be mentioned, for example. From the viewpoint of obtaining the effects of the present invention more efficiently, the electronic device main body is preferably an organic EL element or a solar cell, more preferably an organic EL element, and still more preferably an organic EL lighting element.

  The effects 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 to the following examples.

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

Next, as a smooth layer, a clear hard coat layer with a thickness of 2 μm was formed as follows on the surface of the resin base on which the gas barrier film is to be formed. After applying UV curable resin Opstar (registered trademark) Z7527 manufactured by JSR Corporation to a resin substrate so that the dry film thickness is 2 μm, it is dried at 80 ° C. and then using a high pressure mercury lamp under air. Curing was performed under the conditions of an irradiation energy amount of 0.5 J / cm ² . Thus, a resin substrate with a clear hard coat layer was obtained. Hereinafter, in the present example and the comparative example, the resin substrate with the clear hard coat layer is simply used as the resin substrate for convenience.

(Method of forming non-transition metal M1 containing layer A1)
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 to be formed (that is, a clear hard coat layer 2 μm thick) On the surface of a silicon nitride film having a thickness of 50 nm 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. As a source gas, 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) were introduced into the vacuum chamber. Furthermore, the resin base material temperature was 100 ° C. at the start of film formation. Thus, 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.

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

  The resin substrate was set on the substrate holder in the vacuum chamber of the CVD apparatus to close the vacuum chamber. Next, the inside of the vacuum chamber was evacuated, and when the pressure reached 0.1 Pa, a source gas was introduced. 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 to form a non-transition metal Si-containing layer on the surface of the clear hard coat layer of the resin substrate. A 50 nm thick silicon nitride film 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.

(Method of forming non-transition metal M1 containing layer A3)
The same method is applied 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 in Method A2 for forming the non-transition metal M1 containing layer. Then, a 50 nm thick silicon nitride film 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.

(Method of forming non-transition metal M1 containing layer A4)
A silicon nitride film was formed in the same manner as in Non-Transition Metal M1-Containing Layer Forming Method A2, 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.

(Method of forming non-transition metal M1 containing layer A5)
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.

(Method for forming non-transition metal M1 containing layer A6)
In the formation method A2 of the non-transition metal M1 containing layer, plasma irradiation treatment with light emission (105 nm, 107 nm, 121 nm) with a wavelength of 150 nm or less is further performed on the obtained silicon nitride film using the following apparatus and conditions Similarly, 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 apparatus: Low pressure capacitively coupled plasma processing apparatus (manufactured by U-Tech Co., Ltd.),
Gas: He + H ₂ (H ₂ concentration: 6 vol%),
Total pressure: 19 Pa,
Resin base heating temperature: room temperature,
Input power density: 1.3 W / cm ² ,
Frequency: 13.56 MHz,
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.

(Method of forming non-transition metal M1 containing layer A7)
In the method A5 of forming the non-transition metal M1 containing layer, the silicon nitride film obtained was further subjected to plasma irradiation treatment by the same method as the plasma irradiation treatment in the method A6 of forming the non transition metal M1 containing layer A 300 nm thick silicon nitride film 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.

(Method for forming non-transition metal M1 containing layer A8)
A 50 nm-thick silicon nitride film was formed as a layer containing non-transition metal Si by a magnetron sputtering apparatus (Canon Anelva Co., Ltd .: model EB1100) on the surface of the resin substrate on which the gas barrier film is formed. . 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 film formation was performed by DC sputtering with the ratio of the nitrogen partial pressure to the total pressure being 50%. In addition, the sputtering power supply power was 5.0 W / cm ² , and the deposition pressure was 0.4 Pa. Then, the thickness takes data of the film thickness change with respect to the film formation time in the range of 100 to 300 nm, calculates the thickness to be formed per unit time, and sets the film formation time to become the set thickness. It 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.

(Method of forming non-transition metal M1 containing layer A9)
In the method A8 of forming the non-transition metal M1 containing layer, except that the plasma irradiation treatment is performed on the obtained silicon nitride film by the same method as the plasma irradiation treatment in the method A6 of forming the non transition metal M1 containing layer Similarly, a 50 nm thick silicon nitride film 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 laminated body of the non transition metal M1 containing layer and the resin base material is conveyed, and the formation method of the following transition metal M2 containing layer B1 on the surface of the obtained silicon nitride film The formation of the Nb oxide film was carried out. A gas barrier film 10 was obtained in the same manner as in Comparative Example 1 except that this was done.

(Method of forming transition metal M2 containing layer B1)
A 6 nm thick oxide is formed as a layer containing transition metal M2 on the surface of the silicon nitride film obtained by the formation method A1 of the non-transition metal M1 containing layer using a magnetron sputtering apparatus (Canon Anelva Co., Ltd .: model EB1100) 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 oxygen partial pressure to the total pressure is 12%. The film formation was performed by DC sputtering. In addition, the sputtering power supply power was 5.0 W / cm ² , and the deposition pressure was 0.4 Pa. Then, the thickness takes data of thickness change with respect to the film forming time in the range of 100 to 300 nm, and after calculating the thickness to be formed per unit time, the film forming time is set so as to become the set thickness. It 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.

(Method of forming transition metal M2 containing layer B2)
A niobium oxide film was formed in the same manner as in Method B1 for forming the transition metal M2-containing layer, except that the thickness was 10 nm.

[Example 1: Production of gas barrier film 12]
After the method A2 for forming 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 method for forming the transition metal M2 containing layer on the surface of the obtained silicon nitride film B1 The formation of a niobium oxide film was further carried out. A gas barrier film 12 was obtained in the same manner as in Comparative Example 2 except for the above.

[Example 2: Production of gas barrier film 13]
After the method A3 for forming 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 method for forming the above transition metal M2 containing layer on the surface of the obtained silicon nitride film B1 The formation of a niobium oxide film was further carried out. A gas barrier film 13 was obtained in the same manner as in Comparative Example 3 except for the above.

[Example 3: Production of gas barrier film 14]
After the forming 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 forming method of the above transition metal M2 containing layer on the surface of the obtained silicon nitride film B2 The formation of a niobium oxide film was further carried out. A gas barrier film 14 was obtained in the same manner as in Comparative Example 3 except for the above.

[Example 4: Production of gas barrier film 15]
After the forming 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 forming method of the above transition metal M2 containing layer on the surface of the obtained silicon nitride film The formation of the layer containing the transition metal Nb was further carried out. A gas barrier film 15 having a gas barrier film obtained by forming a layer containing transition metal Nb on the surface of a layer containing non-transition metal Si was obtained in the same manner as in Comparative Example 8 except for the above. .

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 method B1 for forming the transition metal M2 containing layer was changed to the method for forming the layer B3 described below.

(Method for forming transition metal M2 containing layer B3)
A tantalum oxide film having a thickness of 6 nm is similarly used except that a commercially available tantalum target (Ta) is used as the target in the method B1 for forming the transition metal M2 containing layer, and 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.

(Method of forming transition metal M2 containing layer B4)
The same as in Method B1 of forming the transition metal M2 containing layer, except that nitrogen gas is introduced into the process gas, Ar and N ₂ are used as the process gas, and the ratio of nitrogen partial pressure to the total pressure is 50%. Then, a 6 nm thick niobium oxynitride (niobium oxynitride) film 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 Example 2, except that the method B1 for forming the transition metal M2 containing layer was changed to the following method B5.

(Transition metal M2 containing layer B5)
A niobium oxynitride film was formed in the same manner as in Method B1 for forming 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.

(Method of forming non-transition metal M1 containing layer A10)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (Merck Co., Ltd., NN 120-20) and an amine catalyst (N, N, N ', N'-tetramethyl-1, 6-diaminohexane (TMDAH)) A dibutyl ether solution containing 20% by mass of perhydropolysilazane (NAC 120-20, manufactured by Merck Ltd.) mixed in a ratio of 4: 1 (mass ratio) containing 5 parts by mass with respect to 100 parts by mass of perhydropolysilazane The solution was further diluted with dibutyl ether to a concentration of 3% by mass to prepare a coating solution containing non-transition metal Si. The preparation of the coating solution was performed in a glove box.

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

In FIG. 5, reference numeral 1 denotes an apparatus chamber, which supplies a suitable amount of nitrogen and oxygen to the inside from a gas supply port (not shown) and exhausts water vapor from the chamber substantially by exhausting it from a gas discharge port (not shown) The oxygen concentration can be maintained at a predetermined concentration. 2 is a Xe excimer lamp (excimer lamp light intensity: 130 mW / cm ² ) having a double tube structure for irradiating vacuum ultraviolet rays of 172 nm, 3 is a holder of the excimer lamp which doubles as an external electrode, and 4 is a sample stage. The sample stage 4 can be reciprocated horizontally in the apparatus chamber 1 at a predetermined speed (V in FIG. 5) by moving means (not shown). Further, the sample stage 4 can be maintained at a predetermined temperature by heating means (not shown). 5 is a sample in which a polysilazane compound coating layer was formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the coated layer surface of the sample and the excimer lamp tube surface is 3 mm. Reference numeral 6 denotes a light shielding plate, which prevents vacuum ultraviolet rays from being applied to the coating layer of the sample during aging of the Xe excimer lamp 2.

  Here, the energy with which the surface of the sample coating layer is irradiated by the vacuum ultraviolet irradiation treatment was measured using a 172 nm sensor head using a UV integrated actinometer (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd. In the measurement, the sensor head is placed at the center of the sample stage 4 so that the shortest distance between the Xe excimer lamp 2 tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 1 is vacuum ultraviolet Nitrogen and oxygen were supplied so that the oxygen concentration was the same as 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 amount of irradiation energy 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 with 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 is formed. In addition, when the composition distribution in the thickness direction of this layer was measured by XPS analysis described later, the N / Si ratio of this layer was 0.1 as an average value in the thickness direction of the whole layer. However, about 30 nm thick portion of the surface side of the polysilazane modified film on the side opposite to the resin substrate side is a silicon oxynitride (silicon oxynitride) in which nitrogen (N) contained in the original polysilazane remains The film was a film, and the maximum value of the N / Si ratio of that portion 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. A gas barrier film 20 was obtained in the same manner as in Comparative Example 13 except that this was done.

  The manufacturing 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. The XPS analysis conditions are as follows.

(XPS analysis conditions)
Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: monochromated Al-Kα
Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at predetermined thickness intervals with a SiO ₂ converted sputter thickness, to obtain a depth profile in the depth direction. This thickness interval was 1 nm (data for every 1 nm can be obtained in the depth direction)
・ Quantification: The background was determined by the Shirley method, and quantified from the obtained peak area using the relative sensitivity factor method. For data processing, MultiPak manufactured by ULVAC-PHI, Inc. 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).

According to 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 and the region (B) containing the transition metal M2 as the main component of the metal element, the mixed region, and the region (a) It was judged. In addition, from the measurement results, the N / Si ratio (average value in the thickness direction) of the non-transition metal M1 containing layer, the presence or absence of the mixed region, and the composition of the mixed region are M1M2 _x N _y (0.02 ≦ x ≦ 49, y The maximum value (y maximum value) of the existing atomic ratio of the nitrogen atom to the non-transition metal M1 atom at the time of ≧ 0) was determined, and the thickness of the region (a) was determined.

  Here, in the determination of the presence or absence of the mixed region, the atomic ratio of the transition metal M2 to the non-transition metal M1 in the thickness direction of the gas barrier film satisfies the elemental composition within the range of 0.02 to 49 In the case of having a region to be mixed, it is assumed to have a mixed region.

In addition, in the determination of the presence or absence of the region (a), when the composition is indicated by M1M2 _x N _y , the region (a) is included if it has a region satisfying the following formula (1) and the following formula (2) It was a thing.

  In this evaluation, the N / Si ratio (average value in the thickness direction) of the non-transition metal M1 containing layer of the gas barrier films 10 to 18 and 20 is the same except that the non transition metal M2 layer is not formed The sample for measurement which has only the non-transition metal M1 containing layer formed on the resin base material by the method similar to these films was produced, and the measured value was used.

These results are shown in Table 2 below. The y maximum 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.

[Water vapor permeability (water vapor barrier property) evaluation of gas barrier membrane (Ca method)]
(Preparation of a cell for water vapor permeability evaluation)
The water vapor permeability of each gas barrier film having the gas barrier film was evaluated under three conditions according to the following measurement method. Here, two gas barrier films are required to produce one type of water vapor permeability evaluation cell, and six pieces of each gas barrier film are prepared for evaluation under three types of conditions. did.

  The water vapor permeability evaluation cell was produced as follows. First, the surface of the gas barrier film of one gas barrier film was subjected to UV cleaning, and then a 20 μm thick thermosetting sheet adhesive (epoxy resin) 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 into a size of 50 mm × 50 mm, and then placed in a glove box to perform a drying process for 24 hours. In addition, another sheet of the gas barrier film was punched into a size of 50 mm × 50 mm, and then the surface of the gas barrier film of the gas barrier film was subjected to UV cleaning. Subsequently, Ca was vapor-deposited with the size of 20 mm x 20 mm through the mask on the center position of the gas barrier film surface which a gas barrier film has using the vacuum evaporation system made from AIS Co., Ltd. product. 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 sealing resin layer, and the gas barrier property on which Ca is vapor-deposited. The film was placed in contact with the Ca-deposited surface of the film, and adhered by vacuum lamination. Here, vacuum lamination is performed in the state which heated the laminated body (The laminated body of the gas barrier film and the sealing resin layer, and the gas barrier film on which Ca was vapor-deposited) in which adhesion | attachment is performed at 110 degreeC. The Thereafter, the laminated body adhered by vacuum lamination is placed on a hot plate set at 110 ° C. with the side of the gas barrier film to which the sealing resin layer of the laminated body is bonded facing down, and cured for 30 minutes. A water vapor permeability evaluation cell was produced.

  After three cells for water vapor permeability evaluation were produced by the above method for evaluation under three types of conditions, pretreatment necessary for 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: Flexion processing 1»
The 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 center portion of the cell for water vapor permeability evaluation was wound 180 ° around the cylindrical member so that the cylindrical member and the film surface of the gas barrier film to which the sealing resin layer of the water vapor permeability evaluation cell was bonded were in contact. . Then, the center portion of the cell for water vapor permeability evaluation cell is 180 ° to the cylindrical member so that the cylindrical member and the film surface of the gas barrier film on which Ca is vapor-deposited, which is the opposite surface of the water vapor permeability evaluation cell, are in contact. I wound it. The bending process was repeated 100 times by setting the winding operation on the two film surfaces of the water vapor permeability evaluation cell to the cylindrical member as one bending process.

«Condition 3: Flexion processing 2»
A commercially available transparent pressure-sensitive adhesive sheet (20 μm thick) was punched into a size of 50 mm × 50 mm on the surface of the gas barrier film to which the sealing resin layer of the cell for water vapor permeability evaluation was bonded, thickness 125 μm After bonding the PET film of the above, the same bending process as the bending process 1 was performed. In the bending process 2, when the PET film is bonded to one side, in the bending process, the existing positions of the respective gas barrier films of the two gas barrier films are largely deviated from the bending center. 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 under high temperature and high humidity environment)
After the pretreatment necessary for the evaluation of each condition, the water vapor permeability of the gas barrier film of each gas barrier film is obtained by performing the aging treatment in a high temperature and high humidity environment on the water vapor permeability evaluation cell. evaluated. Here, the cell for water vapor permeability evaluation which performed the bending process 2 of the said conditions 3 performed the time-lapse | temporal process in high-temperature, high-humidity environment, after peeling a transparent adhesive sheet and a PET film. Specifically, the water vapor permeability is based on the following index according to the degree of the permeation concentration decrease from the initial permeation concentration with respect to the storage time when the water vapor permeability evaluation cell is stored at 85 ° C. 85% RH environment It was rated by rank. For measurement of transmission density, measurement was made at any four points of the cell using a black and white transmission densitometer TM-5 manufactured by Konica Minolta Co., Ltd., and the average value was calculated. Here, the concentration reduction of 100% represents the transmission concentration in the case of producing a cell for Ca evaluation without performing Ca evaporation. Note that rank 8 or more represents extremely excellent characteristics;
10: 200 hours less than 2% decrease in concentration,
Decrease in concentration by 2% or more and less than 5% in 9: 200 hours,
Decrease in concentration by 5% to less than 10% in 8: 200 hours,
7: 10% or more and less than 20% decrease in concentration in 200 hours,
Decrease in concentration by 20% to less than 50% in 6: 200 hours,
50% or more and less than 80% in 5: 200 hours
The decrease in concentration is less than 80% in 4: 100 hours, and the decrease in concentration is over 80% in 200 hours,
The decrease in concentration is less than 80% in 3:50 hours, and the decrease in concentration is over 80% in 100 hours,
2: Decrease in concentration is less than 80% at 20 hours, decrease by 80% or more at 50 hours,
Decrease in concentration by 80% or more at 1:20 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 has extremely excellent 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 has been confirmed that the property and the remarkably high water vapor barrier property in a high temperature and high humidity environment are compatible.

  Among the production methods of the gas barrier film prepared above, the gas barrier films 12 to 17 in which the non-transition metal M1 containing layer and the non transition metal M2 containing layer were continuously formed by vapor phase film forming method (Examples The manufacturing method of 1-6) was excellent in productivity. Further, 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 does not change the film forming apparatus. In particular, productivity is excellent because film formation can be continuously performed.

<Durability evaluation of organic EL lighting element>
Dark spot evaluation was performed after aging under a high temperature and high humidity environment using an organic EL lighting element manufactured as follows.

[Production of gas barrier film for comparative sealing member]
(Production of gas barrier film 21 for comparison sealing member)
In the production of the gas barrier film 3, the coating solution for forming an organic film obtained by mixing the following is dried on the surface of the 50 nm-thick silicon nitride film obtained by the formation method A3 of the non-transition metal M1 containing layer It applied so that the later thickness might be 1000 nm, and it dried at 80 degreeC, and obtained the coating film. Next, the coated film was cured by irradiation with ultraviolet light at an irradiation energy of 0.5 J / cm ² using a high pressure mercury lamp under 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 method A3 for forming the non-transition metal M1 containing layer. 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 the gas barrier film was measured like other gas barrier films.

«Coating Liquid for Organic Film Formation»
Polymerizable compound: 50 parts by mass of trimethylolpropane triacrylate,
Polymerization initiator: 1 part by mass of ESACURE (registered trademark) KTO 46 (manufactured by Lamberti),
Silane coupling agent: KBM-5013 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts by mass,
Surfactant: 0.5 parts by mass of BYK (registered trademark) 378 (manufactured by Bick Chemie Japan Ltd.),
Methyl ethyl ketone 400 parts by mass.

(Production of gas barrier film 22 for comparison 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 by the same method as the method for forming an organic film and the method for forming a silicon nitride film. 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 the gas barrier film was measured like other gas barrier films.

[Production of Organic EL Lighting Element]
A method as shown below using the 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 Then, the bottom emission type organic EL lighting elements 101 to 106 were manufactured such that the area of the light emitting region was 5 cm × 5 cm.

(Formation of base layer, first electrode)
A well-cleaned alkali-free glass plate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the following compound 118 is put in a tungsten resistance heating boat, and these substrate holder and the resistance heating boat are vacuum evaporation apparatus In the first vacuum chamber. In addition, silver (Ag) was put in a tungsten resistance heating boat and mounted in a second vacuum tank of a vacuum evaporation system.

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

And the base material formed to the base layer was transferred to the 2nd vacuum tank as it was under vacuum, the 2nd vacuum tank was decompressed to 4x10 <^-4> Pa, and the heating boat containing silver was energized and heated. Thereby, the 1st electrode which consists of silver with a thickness of 8 nm was formed at vapor deposition rate 0.1 nm / sec-0.2 nm / sec.

(Organic functional layer to second electrode)
Subsequently, using a commercially available vacuum deposition apparatus, the pressure is reduced to 1 × 10 ⁻⁴ Pa, and then the compound HT-1 is deposited at a deposition rate of 0.1 nm / sec while moving the substrate, and holes of 20 nm Transport layer (HTL) was provided.

  Next, the following compound A-3 (blue light emitting dopant) and the following compound H-1 (host compound) are used so that the compound A-3 linearly becomes 35% by mass to 5% by mass with respect to the film thickness The deposition rate was changed depending on the place, and the deposition rate was changed depending on the place so that the compound H-1 was 65% by mass to 95% by mass, and coevaporation was performed to a thickness of 70 nm to form a light emitting layer.

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

(Solid sealing)
Next, a sealing member was prepared in which a thermosetting sheet-like adhesive (epoxy resin) was bonded as a sealing resin layer on the surface of the gas barrier film of the gas barrier film produced above to a thickness of 20 μm. Using this sealing member, the second electrode was superimposed on the manufactured sample. At this time, the adhesive-formed surface of the sealing member and the organic functional layer surface of the element were continuously superposed so that the end portions of the lead electrodes of the first electrode and the second electrode were exposed.

  Next, the sample was placed in a pressure reducing device, and the superposed base material and the sealing member were pressed and held for 5 minutes under a reduced pressure condition of 90 ° C. and 0.1 MPa. The sample was then returned to atmospheric pressure and heated at 120 ° C. for 30 minutes to cure the adhesive.

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

  Thus, an organic EL lighting element having a light emitting area of 5 cm × 5 cm was produced.

  In addition, each gas barrier film used for preparation of the sealing member in each organic electroluminescent illuminating element is shown in following Table 4.

[Dark spot (DS) evaluation)
(Early 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 four or more pixels were regarded as dark spots, and the generation position (center position) was recorded as the position of the pixels.

(Forced dark spots and evaluation of late spots)
After 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, the number of dark spots having a circle-converted diameter of 200 μm or more was determined, and the number was evaluated as a forced degradation dark spot by a rank based on the following index. Further, when there is a dark spot of 200 μm or more generated at a position not recorded as an initial dark spot, it is considered that there is a delayed dark spot. In the dark spot evaluation, it is assumed that the number of dark spots is rank 5 and the absence of a delayed dark spot represents extremely excellent characteristics;
5: 0 to 9,
4: 10-19,
3: 20 to 29,
2:30 to 49,
1:50 or more,
These results are shown in Table 4 below.

  From the above results, the gas barrier film of the embodiment having the gas barrier film according to the present invention can achieve a high level of water vapor barrier properties required for organic EL elements etc., and a dark spot is generated late. It was confirmed that it could be suppressed. On the other hand, in the gas barrier film of the comparative example having the 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 the occurrence could not be suppressed.

  This application is based on Japanese Patent Application No. 2016-148796 filed on July 28, 2016, the disclosure of which is incorporated in its entirety by reference.

1 equipment chamber,
Xe excimer lamp having a double tube structure that emits vacuum ultraviolet rays of 2 172 nm,
3 Holder for an excimer lamp that doubles as an external electrode,
4 sample stages,
5 A sample in which a polysilazane compound coating layer is formed,
6 shade plate,
V sample stage movement speed,
10, 10 'Layered structure of gas barrier film formed on a film forming object 11, 110 film forming object,
12 non-transition metal M1 containing layer 13 transition metal M2 containing layer,
101 Vacuum plasma CVD system,
102 vacuum chamber,
103 cathode electrode,
105 susceptors,
106 heat medium circulation system,
107 evacuation system,
108 gas introduction system,
109 high frequency power supply,
160 heating and cooling system.

Claims (11)

In the atomic composition distribution profile obtained when performing XPS composition analysis in the thickness direction, a region (a) satisfying the following formula (1) and the following formula (2) when the composition is indicated by M1M2 _x N _y Having a gas barrier film;
  It has a region (A) containing a non-transition metal M1 as a main component of the metal element and a region (B) containing a transition metal M2 as a 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 with the region (B).   The gas barrier film according to claim 1, 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.   The gas-barrier film which has a gas-barrier film of any one of Claims 1-5 on a resin base material.   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 non transition metal M1 as a main component of the metal element in contact with a transition metal M2 containing layer containing transition metal M2 as a main component of the metal element; A method for producing a gas barrier film, comprising
In the atomic composition distribution profile obtained when the XPS composition analysis is performed in the thickness direction of the gas barrier film, when the composition is represented by M1M2 _x N _y , the following formula (1) and the following formula (2) are satisfied A method of producing a gas barrier film having a region (a)
  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 an atmosphere of the vapor phase film forming 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.