WO2017090592A1

WO2017090592A1 - Gas barrier film, and electronic device provided with same

Info

Publication number: WO2017090592A1
Application number: PCT/JP2016/084572
Authority: WO
Inventors: 西尾　昌二; 森　孝博
Original assignee: コニカミノルタ株式会社
Priority date: 2015-11-24
Filing date: 2016-11-22
Publication date: 2017-06-01
Also published as: TW201730009A; JP2019010736A

Abstract

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

Description

Gas barrier film and electronic device equipped with the same

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

As a means for improving the properties of various plastic substrates, particularly gas barrier properties, it is known to form an inorganic gas barrier layer made of silicon oxide or the like on the surface of a plastic substrate (for example, patents) Reference 1).

By the way, various types of electronic devices that have been developed and put into practical use in recent years, such as organic electroluminescence (organic EL) elements, solar cells, touch panels, electronic papers, etc., dislike charge leakage, and therefore form their circuit boards. High moisture barrier properties are required for plastic substrates such as plastic substrates or films for sealing circuit boards. The inorganic gas barrier layer has a higher gas barrier property than an organic film formed of a so-called gas barrier resin or the like, but due to the nature of the film, structural defects such as pinholes and cracks, There is a bond defect (M-OH bond) that becomes a gas passage in the MOM network (M is a metal element), and as a result, this alone is required in the field of organic EL devices. Therefore, the high gas barrier property that has been achieved cannot be satisfied, and further improvement of the gas barrier property is demanded.

As described above, the conventional technology has not yet achieved a high gas barrier property although it is a thin film, which has been required in recent years.

On the other hand, a gas barrier film having a gas barrier layer on a base material causes cracks in the gas barrier layer due to the shrinkage of the base material due to heat under high temperature and high humidity storage, which lowers the gas barrier property. There was also a problem.

JP 2000-255579 A

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

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, the gas barrier layer has a mixed region containing a specific material at least in the thickness direction, It has been found that by setting the glass transition temperature of the constituent material to a specific temperature or higher, it is possible to provide a gas barrier film and an electronic device that have high gas barrier properties and excellent productivity, and have reached the present invention.

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

1. A gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer has a mixed region containing at least a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) in the thickness direction;
A gas barrier film, wherein a glass transition temperature of a constituent material of the substrate is 150 ° C. or higher.

2. 2. The gas barrier film as set forth in claim 1, wherein the constituent material of the base material has a glass transition temperature of 180 ° C. or higher.

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

4). The gas barrier layer includes a region containing the transition metal (M2) or a compound thereof as a main component a (hereinafter referred to as “A region”), and the non-transition metal (M1) or a compound thereof as a main component. a region contained as b (hereinafter referred to as “B region”),
The mixed region is interposed between the A region and the B region, and the mixed region contains a compound derived from the main component a and the main component b. The gas barrier film according to any one of items 1 to 3 above.

5. Any of the first to fourth items, wherein when the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the mixed region satisfies the following relational formula (2): The gas barrier film according to one item.

Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Where, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, a: maximum valence of M1, b: maximum valence of M2 Represents a number.)

6. The gas barrier film according to any one of Items 1 to 5, wherein the non-transition metal (M1) is silicon.

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

8. 8. The electronic device according to item 7, which has a quantum dot-containing resin layer.

9. 8. An electronic device according to item 7, comprising an organic electroluminescence element.

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

The gas barrier film of the present invention is not only remarkably improved in gas barrier properties such as moisture barrier properties, but also excellent in productivity, and thus is useful as a substrate and a sealing layer for various electronic devices. Practical application to organic EL elements can be expected.

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

According to studies by the present inventors, a gas barrier layer is formed by using an oxygen-deficient composition film containing a compound (for example, an oxide) of a non-transition metal (M1) alone, or a transition metal (M2) When a gas barrier layer is formed by using an oxygen-deficient composition film of a compound (for example, an oxide) alone, a tendency to improve the gas barrier property as the degree of oxygen deficiency increases is observed, but a remarkable gas barrier is observed. It did not lead to improvement of sex.

In response to this result, a B region containing a compound (eg, oxide) containing a non-transition metal (M1) as a main component and an A containing a compound (eg, oxide) containing a transition metal (M2) as a main component. When the mixed region containing the non-transition metal (M1) and the transition metal (M2) is interposed between the A region and the B region, and the mixed region has an oxygen deficient composition. It has been found that the gas barrier property is remarkably improved as the degree of oxygen deficiency increases.

As described above, this is because the bond between the non-transition metal (M1) and the transition metal (M2) is more likely to occur than the bond between the non-transition metals (M1) or the transition metal (M2). Thus, it is considered that a high-density structure of the metal compound was formed in the mixed region by setting the mixed region to an oxygen deficient composition.

Sectional drawing which shows schematic structure as an example of the gas barrier film of this invention Graph showing the ratio of the number of atoms to the depth in the thickness direction of the gas barrier layer Sectional drawing which shows schematic structure as an example of the organic EL element which comprised the gas barrier film of this invention Schematic diagram as an example of vacuum ultraviolet irradiation equipment

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

As an embodiment of the present invention, from the viewpoint of storage stability at high temperatures, the glass transition temperature of the constituent material of the base material is preferably 180 ° C. or higher, and the constituent material of the base material is more preferably polyimide.

Further, from the viewpoint of gas barrier performance, the gas barrier layer contains an A region in which the transition metal (M2) or a compound thereof is contained as the main component a, and a non-transition metal (M1) or a compound thereof as the main component b. The mixed region is interposed between the A region and the B region, and the mixed region contains a compound derived from the main component a and the main component b. preferable.

From the viewpoint of blocking the entry of gas (water, oxygen, etc.) molecules, when the composition of the mixed region is represented by the chemical composition formula (1), it is preferable that at least a part of the mixed region satisfies the relational expression (2). .

Further, from the same viewpoint as described above, the non-transition metal (M1) is preferably silicon.

The gas barrier film of the present invention can be suitably provided for an electronic device. Moreover, it is preferable that the said electronic device has a quantum dot containing resin layer. The electronic device preferably includes an organic electroluminescence element.

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

<Gas barrier film>
In FIG. 1, the schematic sectional drawing of the gas barrier film 1 of this invention is shown as an example.
The gas barrier film 1 has a gas barrier layer 3 on a substrate 2.
The gas barrier layer 3 has a mixed region containing at least a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) in at least the thickness direction.

In the present invention, the “region” is an opposing surface formed when the gas barrier layer is divided at a constant or arbitrary thickness on a plane perpendicular to the thickness direction (stacking direction) of the gas barrier layer. The three-dimensional space (region) between the two surfaces is defined, and the composition of the components in the region may be constant in the thickness direction or may gradually change.

In FIG. 1, an example in which the gas barrier layer 3 is provided on only one surface of the base material 2 is shown. However, the gas barrier layer 3 may be provided on both surfaces of the base material 2, or one of the base materials 2 may be provided. A gas barrier layer 3 composed of a plurality of layers may be provided on the surface.

The gas barrier layer 3 includes a region containing the transition metal (M2) or a compound thereof as the main component a (hereinafter referred to as “A region”), a non-transition metal (M1) of group 12 to 14 or a compound thereof. Is contained as a main component b (hereinafter referred to as “B region”), and a mixed region is preferably interposed between the A region and the B region. At this time, the compound derived from the main component a and the main component b is contained in the mixed region.
The gas barrier layer 3 may be composed only of the mixed region without having the A region and the B region.

Here, the “compound derived from the main component a and the main component b” refers to the composite compound formed by the reaction between the main component a and the main component b themselves and the main component a and the main component b.
A “composite oxide” will be described as a specific example of the composite compound. The “composite oxide” is a compound (oxide) formed by chemically bonding the constituent components of the A region and the B region to each other. Say. For example, a compound having a chemical structure in which a niobium atom and a silicon atom form a chemical bond directly or through an oxygen atom.
In the present invention, “composite compound” includes a complex formed by the structural components of the A region and the B region being physically bonded to each other by an intermolecular interaction or the like.
Further, the “main component” refers to a component having the maximum content as an atomic composition ratio. For example, “metal main component” refers to a metal component having the maximum content as an atomic ratio among the metal components in the constituent components.
The “constituent component” refers to a compound constituting a specific region of the gas barrier layer or a simple substance of metal or nonmetal.

Hereinafter, each member constituting the gas barrier film of the present invention will be described in detail.

<Base material>
The base material according to the present invention has a glass transition temperature Tg of a constituent material of 150 ° C. or higher.
Moreover, as a base material, since it can acquire flexibility and light transmittance, it is preferable that it is a resin base material, and also it is preferable that it is a resin film.

As a constituent material of the substrate applicable to the present invention, for example, polyethylene naphthalate (PEN: 155 ° C.), alicyclic polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C. manufactured by ZEON CORPORATION), Polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound described in JP 2001-150584 A: 162 ° C.), polyimide (For example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Inc.), fluorene ring-modified polycarbonate (BCF-PC: for example, compound described in JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: For example, Japanese Patent Laid-Open No. 2000-227603 A compound according to broadcast: 205 ° C.), acryloyl compound (e.g., compounds described in JP-A-2002-80616: 300 ° C. or higher), and the like. The temperature in parentheses indicates the glass transition temperature Tg.
Especially, as a constituent material, a thing with a glass transition temperature of 180 degreeC or more is preferable, and it is more preferable that it is a polyimide.

The glass transition temperature Tg of the substrate can be appropriately adjusted by using an additive or the like.

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

For other types of base materials applicable to the present invention, base material manufacturing methods, and the like, for example, techniques disclosed in paragraphs 0125 to 0136 of JP2013-226758A can be appropriately employed.

<Gas barrier layer>
As described above, the gas barrier layer according to the present invention has a mixed region containing a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) at least in the thickness direction. ing. The mixed region is between the A region containing the transition metal (M2) or a compound thereof as the main component a and the B region containing the non-transition metal (M1) or a compound thereof as the main component b. It may be interposed.

In the mixed region, the gas barrier layer has a ratio of the ratio of the number of atoms of the transition metal (M2) to the non-transition metal (M1) (number of atoms of the transition metal (M2) / number of atoms of the non-transition metal (M1). Is preferably 5 nm or more continuously in the thickness direction in the range of 0.02 to 49.
As for the A region, the B region, the mixed region, and the gas barrier layer, “thickness” or “layer thickness” means a depth in the thickness direction of the gas barrier layer as described later, and XPS analysis is performed. The sputter depth is expressed in terms of SiO ₂ . The “layer thickness” of the gas barrier layer is from the outermost surface side of the gas barrier layer to the interface with the substrate, and the “interface with the substrate” is the gas barrier layer (in the present invention, in the composition analysis by XPS). B region) is the position that is the intersection of the main component distribution curve and the main component distribution curve of the substrate.

In the mixed region, oxygen is preferably contained in addition to the transition metal (M2) and the non-transition metal (M1). The mixed region includes at least a mixture of an oxide of a transition metal (M2) and an oxide of a non-transition metal (M1) or a composite oxide of a transition metal (M2) and a non-transition metal (M1). It is a preferable form that one of them is contained, and a more preferred form is that a composite oxide of a transition metal (M2) and a non-transition metal (M1) is contained.
Here, the “mixture” refers to a product in a state where the constituent components of the A region and the B region are mixed without chemically bonding to each other. For example, a state in which niobium oxide and silicon oxide are mixed without being chemically bonded to each other.

As the gas barrier property of the gas barrier layer, the oxygen permeability measured by a method according to JIS K 7126-1987 when the gas barrier layer was formed on the substrate and calculated as a laminate was 1 × 10 ^−3. ^{^{cm 3 / (m 2 · 24h}} · atm) or less, measured water vapor permeability by the method based on JIS K 7129-1992 (25 ± 0.5 ℃ , 90 ± 2% RH) is 1 × ^{10 -3} g It is preferable that the gas barrier property is not more than / (m ² · 24 h).

(A area)
The A region according to the present invention is a region containing the transition metal (M2) of the Group 5 element of the long-period periodic table or a compound thereof as the main component a. Here, “the compound”, that is, “a compound of transition metal (M2)” refers to a compound containing a transition metal (M2), and examples thereof include transition metal oxides.

Examples of the transition metal (M2) of the Group 5 element in the long-period periodic table include Nb, Ta, and V.
When the transition metal (M2) is a Group 5 element (especially Nb), if the non-transition metal (M1) described later is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

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

(B area)
The region B according to the present invention is a region containing the non-transition metal (M1) of the group 12-14 element of the long-period periodic table or a compound thereof as the main component b. The “compound” here, that is, the “compound of non-transition metal (M1)” refers to a compound containing a non-transition metal (M1), for example, a non-transition metal oxide.

The non-transition metal (M1) is not particularly limited, and any metal of Group 12 to 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. . Among these, as the non-transition metal (M1), Si, Sn or Zn is preferably contained, Si is more preferably contained, and Si alone is particularly preferred.

The thickness of the region B is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm, and more preferably in the range of 50 to 300 nm from the viewpoint of achieving both gas barrier properties and productivity. More preferably within the range.

(Mixed area)
The mixed region according to the present invention is
(1) The gas barrier layer is composed of a plurality of regions having chemical compositions different from each other at least in the thickness direction, and one region (A region) includes transition metal (M2) or a compound thereof (for example, Transition metal oxides (niobium oxide, etc.) are contained, and non-transition metal (M1) or a compound thereof is contained in the other region (B region) directly or indirectly facing the one region. A region containing a compound derived from a transition metal (M2) in the A region and a non-transition metal (M1) in the B region,
Or
(2) When a compound derived from a transition metal (M2) and a non-transition metal (M1) is contained over the entire region in the gas barrier layer, the entire region,
Say.

It is a preferable aspect that the mixed region is continuously present in a thickness of a predetermined value or more (specifically, 5 nm or more) in the thickness direction of the gas barrier layer.
If the mixed region has a thickness of at least about 5 nm, high gas barrier performance can be exhibited. Therefore, even when a very thin gas barrier film is used, high gas barrier performance can be obtained. That is, the gas barrier film of the present invention can be made to be a gas barrier film having excellent bending resistance because the gas barrier layer can be made very thin while gas barrier performance is high.

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

(Oxygen deficient composition)
In the present invention, it is preferable that a part of the composition contained in the mixed region has a non-stoichiometric composition (oxygen deficient composition) in which oxygen is lost.
In the present invention, the oxygen deficient composition is a condition that when the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the composition of the mixed region is defined by the following relational expression (2). It is defined as satisfying. In addition, as the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the mixed region described later is used.

Hereinafter, when no special distinction is necessary, the composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.

As described above, the composition of the composite region of the transition metal (M2) and the non-transition metal (M1) according to the present invention is represented by the chemical composition formula (1). As is apparent from this composition, the composition of the composite region may partially include a nitride structure, and is preferably a composition including a nitride structure from the viewpoint of gas barrier properties.
Here, the maximum valence of the non-transition metal (M1) is a, the maximum valence of the transition metal (M2) is b, the valence of O is 2, and the valence of N is 3. When the composition of the composite region (including a part of the nitride) is a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N. In this case, non-transition metal (M1) And the transition metal (M2) are bonded to either O or N. In the present invention, when two or more kinds are used together as the non-transition metal (M1), or when two or more kinds are used together as the transition metal (M2), the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.

On the other hand, in the mixed region according to the present invention, when (2y + 3z) / (a + bx) <1.0 shown by the relational expression (2), a bond between the non-transition metal (M1) and the transition metal (M2) This means that the total number of O and N bonds is insufficient with respect to the total, and such a state is the above-mentioned “oxygen deficiency”.

In the oxygen deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.

In the present invention, the mixed region is a region where the value of x satisfies 0.02 ≦ x ≦ 49 (0 <y, 0 ≦ z). This is because the value of the ratio of the number ratio of the transition metal (M2) to the non-transition metal (M1) (number of transition metal (M2) atoms / number of non-transition metal (M1) atoms) is 0. This is the same definition as defined as a region having a thickness in the range of .02 to 49 and a thickness of 5 nm or more.
In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a mixed region that satisfies this condition exists in a thickness of a predetermined value or more (5 nm). Therefore, it is thought that it contributes to the improvement of gas barrier properties. In addition, since it is considered that the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2), the more the gas barrier property can be improved, the mixed region is a region satisfying 0.1 ≦ x ≦ 10. It is preferable to include a thickness of 5 nm or more, more preferably include a region satisfying 0.2 ≦ x ≦ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 to a thickness of 5 nm or more. It is further preferable to contain.

As described above, if there is a region satisfying the relationship of (2y + 3z) / (a + bx) <1.0 shown by the relational expression (2) within the range of the mixed region, the effect of improving the gas barrier property is exhibited. However, at least a part of the composition of the mixed region preferably satisfies (2y + 3z) / (a + bx) ≦ 0.9, and satisfies (2y + 3z) / (a + bx) ≦ 0.85. More preferably, it is more preferable to satisfy (2y + 3z) / (a + bx) ≦ 0.8. Here, the smaller the value of (2y + 3z) / (a + bx) in the mixed region, the higher the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and 0.4 ≦ (2y + 3z) / (a + bx) is still more preferable.

In the present invention, the thickness of the mixed region where good gas barrier properties can be obtained is 5 nm or more as the sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and this thickness is 8 nm or more. Is preferably 10 nm or more, more preferably 20 nm or more. The thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.

A gas barrier layer having a mixed region having a specific structure as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.

(Composition analysis by XPS and measurement of the thickness of the mixed region)
The mixed distribution of the gas barrier layer according to the present invention, the composition distribution in the A region and the B region, the thickness of each region, and the like are measured by X-ray photoelectron spectroscopy (XPS) described in detail below. Can be obtained.
Hereinafter, a method for measuring the mixed region, the A region, and the B region by XPS analysis will be described.

The element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the gas barrier layer according to the present invention specifically includes the element concentration of the non-transition metal (M1) (for example, silicon), the transition metal. (M2) Element concentration of niobium (for example, element concentration of oxygen (O), nitrogen (N), carbon (C), etc.) is used in combination with X-ray photoelectron spectroscopy measurement and rare gas ion sputtering such as argon By doing so, it can be created by sequentially performing a surface composition analysis while exposing the inside from the surface of the gas barrier layer.
A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time is roughly correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction. As the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time used in the XPS depth profile measurement is adopted. can do. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

Hereinafter, an example of specific conditions of XPS analysis applicable to the composition analysis of the gas barrier layer according to the present invention will be shown.

・ Analyzer: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background is obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI. The analyzed elements are non-transition metal (M1) (for example, silicon (Si)), transition metal (M2) (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C). It is.
From the obtained data, the composition ratio is calculated, the ratio of the atomic ratio of the transition metal (M2) and the non-transition metal (M1), and the non-transition metal (M1) and the transition metal (M2) coexist. The range in which the value of (the atomic ratio of transition metal (M2) / the atomic ratio of non-transition metal (M1)) is 0.02 to 49 is determined, this is defined as a mixed region, and the thickness is determined . The thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO ₂ .

Below, the specific example of the mixing area | region in the gas barrier layer which concerns on this invention is demonstrated using figures.
FIG. 2 is a graph for explaining an element profile and a mixed region when the composition distribution of the non-transition metal (M1) and the transition metal (M2) in the thickness direction of the gas barrier layer is analyzed by the XPS method.
In FIG. 2, elemental analysis of non-transition metal (M1), transition metal (M2), O, N, and C is performed in the depth direction from the surface of the gas barrier layer (surface opposite to the base material). sputtering the axial depth: the (nm SiO ₂ equivalent), the content of the vertical axis with non-transition metals (M1) and transition metal (M2) (at%) is a graph showing a.
From the base material side, a B region which is an elemental composition mainly composed of a non-transition metal (M1) (for example, Si) as a metal is shown, and a transition metal (as a metal toward the gas barrier layer surface side in contact with this) M2) A region which is an elemental composition mainly composed of niobium (for example, niobium) is shown. In the mixed region, the value of the ratio of the number of atoms of the transition metal (M2) and the non-transition metal (M1) (the ratio of the number of atoms of the transition metal (M2) / the number of atoms of the non-transition metal (M1)) is 0. A region having an elemental composition within a range of 0.02 to 49, a region that overlaps a part of the A region and a part of the B region, and has a thickness of 5 nm or more.

<Method for forming each region>
(Method for forming region A)
A method for forming the A region containing the transition metal (M2) is not particularly limited, and for example, a conventionally known vapor deposition method using an existing thin film deposition technique can be used to efficiently form the mixed region. It is preferable from the viewpoint of formation.

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

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

Also, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable.

As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, oxynitrides, oxycarbides, etc. are formed. can do. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected depending on the sputtering apparatus, the material of the film, the thickness, and the like.

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

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

(Method for forming region B)
There is no restriction | limiting in particular as a formation method of B area | region containing a non-transition metal (M1), For example, a vapor-phase film-forming method can be used by a well-known method. The vapor deposition method is not particularly limited. For example, chemical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, chemistry such as plasma CVD, ALD, and the like. A vapor deposition (CVD) method may be mentioned. Among these, it is possible to form a film without damaging the functional element, and since it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method. M1) can be used as a target.

Further, as another method, a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal (M1) is one of the preferable methods.

In the present invention, “polysilazane” applicable to the formation of the B region is a polymer having a silicon-nitrogen bond in the structure, and includes SiO ₂ , Si _{3 made of} Si—N, Si—H, NH, or the like. N is ₄ and both of the intermediate solid solution _SiO x _N preceramic inorganic polymers, such as _y.

In order to form the B region constituting the gas barrier layer using polysilazane so as not to impair the planarity of the above-described base material, the relatively Polysilazanes that can be modified to silicon oxide, silicon nitride or silicon oxynitride at low temperatures are preferred.
Examples of such polysilazane include compounds having a structure represented by the following general formula (1).

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

In the present invention, perhydropolysilazane (PHPS), in which all of R ₁ , R _2, and R ₃ are hydrogen atoms, is particularly preferred from the viewpoint of denseness as a thin film in the B region.

On the other hand, organopolysilazanes in which hydrogen atoms bonded to Si are partially substituted with alkyl groups or the like have an alkyl group such as a methyl group, so that the adhesion to an adjacent substrate is improved, and it may be hard. A ceramic film made of polysilazane can be tough, and even when the B region is made thicker, it is preferable in that the generation of cracks is suppressed.

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

The molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn) and varies depending on the molecular weight of a liquid or solid substance.
These polysilazane compounds are commercially available in a solution state dissolved in an organic solvent, and a commercially available product can be used as a polysilazane compound-containing coating solution as it is.

Other examples of polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially No. 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (Japanese Patent Laid-Open No. 6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (Japanese Patent Laid-Open No. 6-299118). No. 1), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7- 1969 6 No.), and the like.

Other details of polysilazane include, for example, paragraphs 0024 to 0040 of JP2013-255910A, paragraphs 0037 to 0043 of JP2013-188942, and paragraphs 0014 to 0021 of JP2013-151123A. Refer to the contents described in paragraphs 0033 to 0045 of JP 2013-052569 A, paragraphs 0062 to 0075 of JP 2013-129557 A, paragraphs 0037 to 0064 of JP 2013-226758 A, and the like. Can be applied.

As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Suitable organic solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, or ethers such as aliphatic ethers and alicyclic ethers. Can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
These organic solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.

The concentration of polysilazane in the coating liquid containing polysilazane varies depending on the thickness of the target gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.

In addition, an amine or a metal catalyst may be added to the coating liquid containing polysilazane in order to promote modification to silicon oxide, silicon nitride, or silicon oxynitride. For example, a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to. Moreover, these commercial items may be used independently and may be used in mixture of 2 or more types.

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

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

(Additive elements)
An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane. By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the coating composition can be changed to a stable composition close to SiO ₂ after drying. it can.

Examples of metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.
In particular, Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.

Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate). Acetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) Ken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.) It is possible.

In addition, when using these compounds, it is preferable to mix with the coating liquid containing polysilazane in inert gas atmosphere. This is to prevent these compounds from reacting with moisture and oxygen in the atmosphere and causing intense oxidation.
When these compounds and polysilazane are mixed, the temperature is preferably raised to 30 to 100 ° C. and maintained for 1 minute to 24 hours with stirring.
The content of the additive metal element in the polysilazane-containing layer constituting the gas barrier layer according to the present invention is preferably in the range of 0.05 to 10 mol% with respect to the silicon (Si) content of 100 mol%, More preferably, it is in the range of 0.5 to 5 mol%.

(Modification process)
In the formation of the B region using polysilazane, it is preferable to perform a modification treatment after forming the polysilazane-containing layer.
The modification treatment is treatment for imparting energy to polysilazane and converting part or all of it into silicon oxide or silicon oxynitride.

As the modification treatment in the present invention, a known method based on the conversion reaction of polysilazane can be selected, and examples thereof include known plasma treatment, plasma ion implantation treatment, ultraviolet irradiation treatment, vacuum ultraviolet irradiation treatment and the like. In the present invention, a conversion reaction using plasma, ozone or ultraviolet light that can be converted at a low temperature is preferable. A conventionally known method can be used as the conversion reaction by plasma or ozone. In the present invention, a gas barrier layer is applied by applying a vacuum ultraviolet ray irradiation treatment in which a coating film of a polysilazane-containing coating solution of a coating method is provided on a substrate, and a modification treatment is performed by irradiating a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less. The method of forming is preferred.

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

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

For details of these reforming treatments, for example, paragraphs 0055 to 0091 of JP2012-086394A, paragraphs 0049 to 0085 of JP2012-006154A, paragraphs 0046 to 0074 of JP2011-251460A, for example. Etc. can be referred to.

(Method for forming mixed region)
As a method of forming the mixed region, there is a method of forming the mixed region between the A region and the B region by appropriately adjusting the respective formation conditions when forming the A region and the B region as described above. preferable.

When forming the B region by the above-described vapor deposition method, for example, the ratio of the non-transition metal (M1) and oxygen in the deposition material, the ratio of the inert gas and the reactive gas during the deposition, A mixed region is formed by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation. can do.
When forming the B region by the above-described coating film forming method, for example, a film forming raw material type (polysilazane type or the like) containing a non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, a drying temperature, The mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method and reforming conditions.

When the A region is formed by the above-described vapor deposition method, for example, the ratio of the transition metal (M2) and oxygen in the deposition material, the ratio of the inert gas and the reactive gas during the deposition, and the deposition The mixed region is formed by adjusting one or more conditions selected from the group consisting of the amount of gas supplied, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation. be able to.

Note that, in order to control the thickness of the mixed region by the above-described method, the formation conditions of the method of forming the A region and the B region can be adjusted as appropriate. For example, when forming the A region by a vapor deposition method, a desired thickness can be obtained by controlling the deposition time. In addition to this, a method of directly forming a mixed region of the non-transition metal (M1) and the transition metal (M2) is also preferable.

As a method for directly forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2). One-way sputtering using a composite target made of an oxide as a sputtering target may be used.
In addition, the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be. With respect to a method for producing these sputtering targets and a method for producing a thin film made of a composite oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP Reference can be made to the descriptions in Japanese Patent Application Laid-Open No. 2013-047361.
The film forming conditions for performing the co-evaporation method include the ratio of transition metal (M2) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, Examples include one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation. These film formation conditions (preferably oxygen partial pressure) are By adjusting, a thin film having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area | region.

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

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

As an anchor coat agent used for the anchor coat layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. are used alone. Or it can use in combination of 2 or more types.

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

The anchor coat layer can also be formed by a vapor deposition method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Further, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor deposition method, a gas generated from the substrate side is reduced. An anchor coat layer can also be formed for the purpose of blocking to some extent and controlling the composition of the inorganic thin film.

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

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

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

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

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

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

The formation method of the clear hard coat layer is not particularly limited, but it is preferably formed by a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition method.

In the formation of the clear hard coat layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above active energy ray-curable resin as necessary. Further, regardless of the position of the clear hard coat layer, an appropriate resin or additive may be used in any clear hard coat layer in order to improve the film formability and prevent the generation of pinholes in the film.

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

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

Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, a QD film having a quantum dot (QD) -containing resin layer, an organic electroluminescence element (organic EL element), and a liquid crystal display. An element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like can be given. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

<Quantum dot (QD) film>
The gas barrier film of the present invention can be applied to a QD film containing quantum dots.

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

(Quantum dot)
In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.

Therefore, it is known that quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.

The quantum dot contained in the QD-containing resin layer may be a known one, and can be generated using any known method. For example, suitable quantum dots and methods for forming them include US Pat. No. 6,225,198, US Patent Application Publication No. 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901, And those described in US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155. .

Quantum dots are generated from any suitable material, preferably an inorganic material, more preferably an inorganic conductor or semiconductor material. Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.

Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si ₃ N ₄ , Ge ₃ N ₄ , Al ₂ O ₃ , _{(Al, Ga, In) 2} (S, Se, Te) 3, Al 2 O, and include but are more than one suitable combination of such semiconductor, and the like.

In the present invention, the following core / shell type quantum dots, for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS, and the like can be preferably used.

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

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

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

<< Organic EL element >>
A typical example of an electronic device to which the gas barrier film of the present invention is applied is an organic EL element as shown in FIG. As shown in FIG. 3, the organic EL element 10 covers a support 11 with a pair of

electrodes

12 and 14, an organic functional layer 13 positioned between the pair of

electrodes

12 and 14, and the organic functional layer 13. Sealing material 15 to be provided. The gas barrier film 1 of the present invention can be applied as the support 11.

The organic functional layer 13 includes at least a light emitting layer, and includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like as necessary.
The light-emitting layer contains a light-emitting organic compound, an organometallic complex, or the like, and is directly injected from one electrode (anode) or from the anode through a hole transport layer, and the other. Electrons directly injected from the electrode (cathode) or electrons injected through the electron transport layer or the like emit light by recombination.

The organic functional layer 13 and the

electrodes

12 and 14 are liable to deteriorate due to the intrusion of gas such as oxygen and water in the atmosphere. The organic EL element 10 includes the above-described gas barrier film 1 as the support 11 in order to suppress a decrease in light emission performance due to such deterioration of the organic functional layer 13 and the like, but a gas barrier as the sealing material 15. The film 1 can also be provided.

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

[Example 1]
<< Production of gas barrier film >>
Gas barrier films 101 to 109 were produced according to the following method.

<Preparation of gas barrier film 101>
(1) Preparation of base material Clear hard coat layer 1 (back side) on both sides of a 100 μm thick polyethylene terephthalate film (Lumirror (registered trademark) U48, abbreviated as PET film) manufactured by Toray Industries, Inc. ) And clear hard coat layer 2 (gas barrier layer forming surface side) were formed by the following method.

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

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

(2) Formation of gas barrier layer (formation of film containing non-transition metal (M1))
A film containing a non-transition metal (M1) was formed on the surface of the base material on which the clear hard coat layer 2 was formed by a vapor phase method / sputtering (a magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100). The sputtering apparatus used is capable of two-way simultaneous sputtering.

Here, a polycrystalline Si target was used as a target, and a mixed gas of Ar and O ₂ was used as a process gas to form a film having a thickness of 55 nm by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Film formation was performed by adjusting the oxygen partial pressure so that the composition was SiO ₂ . In addition, film formation using a glass substrate is performed in advance, and the condition of the composition is determined by adjusting the oxygen partial pressure. The condition where the composition near the depth of 10 nm from the surface layer becomes SiO ₂ is found, and the condition is applied. did. As for the thickness, data on the change in thickness with respect to the film formation time is obtained within a range of 100 to 300 nm, the film formation per unit time is calculated, and then the film is formed to have a set thickness. Set the time.

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

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

As a target, a commercially available metal Nb target was used, and a mixed gas of Ar and O ₂ was used as a process gas, and a film was formed to a thickness of 10 nm by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was 12% under the film forming conditions. It should be noted that, after film formation using a glass substrate material in advance, the thickness change data with respect to the film formation time is taken under the film formation conditions, the thickness to be formed per unit time is calculated, The film formation time was set so that

Thus, a gas barrier layer having a layer thickness of 65 nm was formed.

(3) XPS Analysis of Gas Barrier Layer A composition distribution profile in the thickness direction was measured from the surface side of the gas barrier layer by XPS analysis. The XPS analysis conditions are as follows. The sample used for the analysis was a sample stored in an environment of 20 ° C. and 50% RH after sample preparation.

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

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

<Preparation of gas barrier films 102-104>
In the production of the gas barrier film 101, gas barrier films 102 to 104 were produced in the same manner except that the base material was changed as shown in Table 1.

PEN: Teonex manufactured by Teijin Limited PES: Sumika Excel 4010GL30 manufactured by Sumitomo Chemical Co., Ltd.
PI: Neoprim, manufactured by Mitsubishi Gas Chemical Co., Ltd.

<Preparation of gas barrier film 105>
In the production of the gas barrier film 104, the target for forming the film containing the non-transition metal (M1) was changed to aluminum oxide (refractive index 1.63), and the film was formed to have a thickness of 70 nm. In the same manner, a gas barrier film 105 was produced.

<Preparation of gas barrier films 106-108>
In the production of the gas barrier films 102 to 104, the gas barrier property was similarly changed except that the target for forming the film containing the transition metal was changed to a metal Ta target and formed to a thickness of 10 nm. Films 106 to 108 were produced.

<Preparation of gas barrier film 109>
In the production of the gas barrier film 104, a gas barrier film 109 was produced in the same manner except that the gas barrier layer was formed as follows.

(Formation of gas barrier layer)
On the surface side of the base material on which the clear hard coat layer 2 is formed, a polycrystalline Si target and a metal Nb target are used as targets, Ar and O ₂ are used as process gases, and a co-sputtering method is performed by a DC method. A gas barrier layer was formed by performing original co-sputtering. The power supply power in the polycrystalline Si target and the power supply power in the metal Nb target were adjusted so that the oxygen partial pressure was 18% and the atomic ratio of Si and Nb in the film was the same. The film formation time was set so that the layer thickness was 50 nm.

<Evaluation>
About each produced gas-barrier film, water vapor permeability and preservability were evaluated as follows.
The evaluation results are shown in Table 1.

<Measurement of water vapor transmission rate>
According to the following measurement method, the permeated water amount (water vapor permeability) of each produced gas barrier film was measured to evaluate the water vapor barrier property.
In addition, regarding the gas-barrier film of this invention, although the measuring method of water vapor permeability is not specifically limited, In this Example, Ca method was employ | adopted as a water vapor permeability measuring method.

(Device used)
Vapor deposition device: JEE-400, a vacuum vapor deposition device manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M

(Evaluation materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)

(Preparation of water vapor barrier property evaluation cell)
Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), metal calcium was vapor deposited by masking portions other than the portion (12 mm × 12 mm in 9 locations) of the gas barrier layer of the sample. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After sealing with aluminum, the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass having a thickness of 0.2 mm is provided on the aluminum vapor deposition surface via a sealing UV curable resin (manufactured by Nagase ChemteX). Were bonded together, and the resin was cured and adhered, followed by main sealing, thereby producing a water vapor barrier property evaluation cell.

Then, using the constant temperature and humidity oven, the obtained evaluation cell was stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of corrosion of metallic calcium was determined based on the method described in JP-A-2005-283561. From this, the amount of water permeated into the cell (g / (m ² · 24 h)) was calculated.
In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium on a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample In the same manner, the cell was stored under high temperature and high humidity of 60 ° C. and 90% RH, and it was confirmed that corrosion of metallic calcium did not occur even after 1000 hours.

<Evaluation of storage stability (crack evaluation)>
About the produced gas barrier film, after storing a sample of size 300 mm × 300 mm in an environment of 85 ° C. and 85% RH for 14 days, the permeated water content (water vapor permeability) was measured by the same method as above, and before and after storage. From the change in permeated water amount, the degree of deterioration resistance was calculated according to the following formula, and the storage stability was evaluated according to the following criteria.
Deterioration resistance = (permeated water amount after storage / permeated water amount before storage) × 100 (%)

5: Deterioration resistance is 98% or more.
4: Deterioration resistance is 95% or more and less than 98%.
3: Deterioration resistance is 90% or more and less than 95%.
2: Deterioration resistance is 80% or more and less than 90%.
1: Deterioration resistance is less than 80%.

<Summary>
As is clear from Table 1, it was confirmed that the gas barrier film of the present invention was superior in water vapor permeability and storage stability as compared with the gas barrier film of the comparative example.
From the above, the gas barrier layer has a mixed region containing at least the group 5 transition metal and the group 12 to 14 non-transition metal (M1) in the thickness direction, and the glass transition of the constituent material of the base material It can be seen that a temperature of 150 ° C. or higher is useful for providing a gas barrier film having high gas barrier properties and excellent productivity.

[Example 2]
<< Production of gas barrier film >>
Gas barrier films 201 to 205 were prepared according to the following method.

<Preparation of gas barrier film 201>
(1) Preparation of base material Clear hard coat layer 1 (back side) on both sides of a 100 μm thick polyethylene terephthalate film (Lumirror (registered trademark) U48, abbreviated as PET film) manufactured by Toray Industries, Inc. ) And clear hard coat layer 2 (gas barrier layer forming surface side) were formed by the following method.

(2) Formation of gas barrier layer (formation of film containing non-transition metal (M1))
A polysilazane containing Si was used as the non-transition metal (M1), and a film containing the non-transition metal (M1) was formed by a coating / modification method as follows.

First, a dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6) -Dihydrohexane (TMDAH))-containing perhydropolysilazane 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1 (mass ratio) and further dried. In order to adjust the film thickness, it was appropriately diluted with dehydrated dibutyl ether to prepare a coating solution.

Next, the above coating solution was applied by spin coating in a nitrogen atmosphere in the glove box so that the dry film thickness was 55 nm, and dried at 80 ° C. for 10 minutes.

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

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

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

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

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

As a target, a commercially available metal Nb target was used, and a mixed gas of Ar and O ₂ was used as a process gas, and the film was formed to a thickness of 9 nm by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was 12% under the film forming conditions. It should be noted that, after film formation using a glass substrate material in advance, the thickness change data with respect to the film formation time is taken under the film formation conditions, the thickness to be formed per unit time is calculated, The film formation time was set so that

Thus, a gas barrier layer having a layer thickness of 64 nm was formed.

(3) XPS analysis of gas barrier layer XPS analysis was performed in the same manner as in Example 1 for the gas barrier layer formed by the above method.

(4) Calculation of oxygen deficiency index (2y + 3z) / (a + bx) in the mixed region The value of (2y + 3z) / (a + bx) in the thickness direction in the mixed region was calculated in the same manner as in Example 1.

<Preparation of gas barrier films 202 to 204>
In the production of the gas barrier film 201, gas barrier films 202 to 204 were produced in the same manner except that the base material was changed as shown in Table 2.

<Preparation of gas barrier film 205>
In the production of the gas barrier film 204, the gas barrier film 205 was similarly formed except that the target for forming the film containing the transition metal was changed to a metal Ta target and formed to a thickness of 10 nm. Was made.

<Evaluation>
About each produced gas-barrier film, it carried out similarly to Example 1, and evaluated water vapor permeability and preservability.
The evaluation results are shown in Table 2.

<Summary>
As is clear from Table 2, it was confirmed that the gas barrier film of the present invention was superior in water vapor permeability and storage stability compared to the gas barrier film of the comparative example.

The present invention can be particularly suitably used for providing a gas barrier film having high gas barrier properties and excellent productivity.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Base material 3 Gas barrier layer 10 Organic EL element 11

Support body

12, 14 Electrode 13 Organic functional layer 15 Sealing material 100 Vacuum ultraviolet light irradiation apparatus 101 Apparatus chamber 102 Xe excimer lamp 103 Holder 104 Sample stage 105 Sample 106 light shielding plate

Claims

A gas barrier film having a gas barrier layer on a substrate,
The gas barrier layer has a mixed region containing at least a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) in the thickness direction;
A gas barrier film, wherein a glass transition temperature of a constituent material of the substrate is 150 ° C. or higher.
The gas barrier film according to claim 1, wherein a glass transition temperature of the constituent material of the substrate is 180 ° C or higher.
The gas barrier film according to claim 2, wherein the constituent material of the substrate is polyimide.
The gas barrier layer is composed of a group 5 transition metal (M2) or a compound containing the compound as a main component a (hereinafter referred to as “A region”) and a group 12-14 non-transition metal (M1). Or a region containing the compound as the main component b (hereinafter referred to as “B region”),
The mixed region is interposed between the A region and the B region, and the mixed region contains a compound derived from the main component a and the main component b. The gas barrier film according to any one of claims 1 to 3.
The composition of the said mixing area | region is represented by following chemical composition formula (1), At least one part of the said mixing area | region satisfy | fills the following relational expression (2), Any one of Claim 1 to 4 The gas barrier film according to one item.
Chemical composition formula (1): (M1) (M2) x O y N z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Where, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, a: maximum valence of M1, b: maximum valence of M2 Represents a number.)
The gas barrier film according to any one of claims 1 to 5, wherein the non-transition metal (M1) is silicon.
An electronic device comprising the gas barrier film according to any one of claims 1 to 6.
The electronic device according to claim 7, further comprising a quantum dot-containing resin layer.
The electronic device according to claim 7, further comprising an organic electroluminescence element.