JP6737279B2 - Electronic device and method for sealing electronic device - Google Patents

Description

The present invention relates to an electronic device and a method for sealing an electronic device. More specifically, the present invention relates to an electronic device including an encapsulating layer having high gas barrier performance, and an electronic device encapsulating method using the encapsulating layer.

An electronic device, particularly an organic electroluminescence device (hereinafter, also referred to as an organic EL device or an organic EL element) is formed with a sealing layer for covering the element in order to prevent deterioration of an organic material or an electrode used due to moisture. To be done. The sealing layer for the organic EL element has a water vapor transmission rate (WVTR) of 10 ⁻⁵ to 10 ⁻⁶ g/m ² ·24h on the order of 25±0.5° C. and 90±2% RH. It is said that a very high gas barrier property is required.

Conventionally, a gas barrier film using a vapor deposition apparatus has been manufactured as a gas barrier substrate. Particularly, a gas barrier film on the order of 10 ⁻³ g/m ² ·24 h is manufactured by a physical vapor deposition (PVD) film forming apparatus such as a sputtering method.

Further, a laminated gas barrier film has been studied in order to obtain a transparent gas barrier substrate having low water vapor permeability and high light transmittance. For example, in Patent Document 1, Group A (including tantalum (Ta), niobium (Nb), etc.) oxides, nitrides, oxynitrides, and Group B (boron (B), aluminum (Al), silica (Si). ), titanium (Ti), tantalum (Ta), etc.) oxides, nitrides, oxynitrides, etc. are laminated by sputtering or the like to obtain a laminated gas barrier film. However, the gas barrier performance is not sufficient, and only a gas barrier film on the order of 10 ⁻² g/m ² ·24 h is obtained.

Further, for example, in Patent Document 2, a silicon nitride (SiN) film (thickness 2 μm) formed by a CVD (chemical vapor deposition) film forming method and a polysilazane coating film (thickness 500 nm) are disclosed. A combined sealing film has been proposed. However, since the polysilazane coating film is formed only by coating and drying and uses only the moisture absorption ability, it has an apparent water vapor barrier function due to the moisture absorption ability as the initial performance, but after the moisture absorption ability is saturated. Loses its ability to block water vapor and has limited effects. Further, in order to form a SiN film having a thickness of 2 μm, a process requiring a long film formation time is required, and the required gas barrier property cannot be satisfied only with the SiN film having a thickness of 2 μm.

Further, in the method as described above, the device performance is remarkably deteriorated because the device is exposed to high temperature or strong ultraviolet (UV) for a long time. Therefore, an electronic device provided with an encapsulating layer having a gas barrier property that minimizes the time of exposure to high temperature or ultraviolet (UV) and a method for encapsulating an electronic device using the encapsulating layer are provided. is necessary.

Furthermore, a method of forming a laminated film of any of an organic compound and an inorganic compound (metal oxide, metal nitride, metal oxynitride, metal carbide, etc.) by a vapor deposition method has been investigated, but the water vapor permeability is low. However, the sealing of the organic EL element was not satisfied.

Therefore, as a sealing layer for an organic EL element, a sealing layer having high productivity and high gas barrier performance has been demanded.

JP, 2005-035128, A JP, 2013-200985, A

The present invention has been made in view of the above problems and circumstances, and a problem to be solved is an electronic device including a sealing layer having high gas barrier performance, and sealing of an electronic device using the sealing layer. Is to provide a method.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this inventor WHEREIN: In the process of examining the cause etc. of said problem, the sealing layer of an electronic device is a 1st gas barrier layer containing the oxide of specific metal (M1). A laminated body of a second gas barrier layer containing an oxide of a specific metal (M2), or a gas barrier layer containing a composite oxide of the metal (M1) and the metal (M2). It has been found that an electronic device including a sealing layer having high gas barrier performance can be obtained by having a region containing the composite oxide.

That is, the above-mentioned subject concerning the present invention is solved by the following means.

1. An electronic device comprising a pair of electrodes on a base material, an organic functional layer including at least one light emitting layer between the electrodes, and a sealing layer arranged on the organic functional layer, wherein the sealing layer is A first gas barrier layer containing an oxide of a non-transition metal (M1) of Groups 12 to 14, and an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer. laminate der of the second gas barrier layer which is, and a part of the thickness direction of the laminate region containing the composite oxide of the non-transition metals (M1) and the transition metal (M2) or there is a laminate existing, or the or a gas barrier layer containing a composite oxide of non-transition metals (M1) and the transition metal (M2), or have a region containing the composite oxide An electronic device characterized by.

2 . The gas barrier layer or region containing the complex oxide is (M1)(M2) _x O _y N _z, where M1 is a non-transition metal, M2 is a transition metal, O is O and nitrogen is N. 2. The electronic device according to item 1, which contains the represented complex oxide and the composition of the complex oxide satisfies the following relational expression (1).

Relational expression (1) (2y+3z)/(a+bx)<1.0
(However, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, 0.02≦x≦49, 0<y, 0≦z, a : Represents the maximum valence of M1, b: represents the maximum valence of M2.)
3 . 3. The electronic device according to item 1 or 2, wherein the layer containing the non-transition metal (M1) contains polysilazane and a modified polysilazane.

4 . The electronic device according to any one of items 1 to 3, wherein the transition metal (M2) is selected from niobium (Nb), tantalum (Ta), and vanadium (V). ..

5 . The electronic device according to any one of items 1 to 4, wherein at least one organic polymer layer is laminated on the functional element.

6 . The electronic device according to any one of items 1 to 5 , wherein the functional element has a pair of electrodes and an organic functional layer including at least one light emitting layer between the electrodes. ..

7 . A method for sealing an electronic device, comprising forming a functional element and a sealing layer for sealing the functional element on a base material, wherein at least one non-transition metal of Group 12 to 14 is used as the sealing layer. A laminate of a first gas barrier layer containing an oxide of (M1) and a second gas barrier layer containing an oxide of a transition metal (M2) arranged in contact with the first gas barrier layer. And a laminate in which a region containing a complex oxide of the non-transition metal (M1) and the transition metal (M2) is present in a part of the thickness of the laminate , or the non-transition A gas barrier layer containing a composite oxide of a metal (M1) and the transition metal (M2) or a region containing the composite oxide is formed by a vapor phase film forming method or a coating method. Electronic device sealing method.

8 . As the sealing layer, to the functional element side, sealed electronic device according to paragraph 7, which comprises forming a first gas barrier layer containing an oxide of the non-transition metal (M1) How to stop.

9 . A second gas barrier layer containing the oxide of the transition metal (M2) is formed on the first gas barrier layer containing the oxide of the non-transition metal (M1) by a vapor phase film forming method. The method for encapsulating an electronic device according to item 7 or 8 , wherein the method is formed.

10 . The first gas barrier layer containing an oxide of the non-transition metal (M1) contains polysilazane and a modified polysilazane, and the modified polysilazane is applied with a coating solution containing polysilazane. The method for sealing an electronic device according to any one of items 7 to 9 , wherein the method is formed by irradiating vacuum ultraviolet light.

By the above means of the present invention, it is possible to provide an electronic device including a sealing layer having high gas barrier performance, and a method for sealing an electronic device using the sealing layer.

The mechanism of action or mechanism of action of the present invention has not been clarified, but is presumed as follows.

The present invention is an electronic device including a sealing layer having a high gas barrier property applicable to an organic EL element, the sealing layer containing an oxide of a non-transition metal of group 12 to 14 (M1). It is a laminated body of a first gas barrier layer containing and a second gas barrier layer containing an oxide of a transition metal (M2) arranged in contact with the first gas barrier layer, or It is a gas barrier layer containing a composite oxide of a transition metal (M1) and the transition metal (M2), or a region containing the composite oxide.

In the case where the gas barrier layer is the laminated body, when the first gas barrier layer and the second gas barrier layer are vapor-phase deposited, the non-transition metal (M1) and the transition metal ( M2) is present as a composition at the same time, a region is formed, and when the region becomes a region containing a metal oxide having a composition lacking oxygen with respect to the stoichiometric composition, a metal oxide is formed. It is considered that a region having a high-density bond is formed to exhibit a high gas barrier property.

In the case of the gas barrier layer containing the complex oxide of the non-transition metal (M1) and the transition metal (M2), or the region containing the complex oxide, for example, Si (or SiO _x ) and Nb (or NbO) are used. _x ) is simultaneously sputtered as a sputtering target (also referred to as co-deposition or co-sputtering), and oxygen is introduced as a reactive gas to form a complex oxide of Si and Nb in a stoichiometric manner. When the film is formed under the condition that oxygen is less than the composition, the obtained composite oxide is considered to have a structure having a Si—Nb bond. As a result, in the case where the composite oxide having a stoichiometric composition has a composition in which oxygen is deficient so as to satisfy the above relational expression (1), a composite oxide having a high density of metals is bonded. It is presumed that it becomes a gas barrier layer containing or a region containing the composite oxide and exhibits high gas barrier properties.

Schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention. Schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention. Schematic cross-sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention. Schematic cross-sectional view showing an electronic device including a sealing layer having an organic polymer layer and a gas barrier layer according to another embodiment of the present invention. Schematic cross-sectional view showing an electronic device including a sealing layer having an organic polymer layer and a gas barrier layer according to another embodiment of the present invention. A graph for explaining the element profile and the composite composition region when the composition distribution of the non-transition metal (M1) and the transition metal (M2) in the thickness direction of the sealing layer is analyzed by the XPS method. Schematic diagram of an evaluation device for WVTR measurement Schematic sectional view showing an example of a vacuum ultraviolet light irradiation apparatus applicable to the formation of the sealing layer according to the present invention

The electronic device of the present invention is an electronic device including a pair of electrodes on a base material, an organic functional layer including at least one light emitting layer between the electrodes, and a sealing layer disposed on the organic functional layer. Then, the sealing layer includes a first gas barrier layer containing an oxide of a non-transition metal (M1) of Group 12 to 14 and a transition metal (which is disposed in contact with the first gas barrier layer). laminate der of the second gas barrier layer containing an oxide of M2) is, and the portion of the thickness direction of the laminate, the non-transition metal (M1) and the transition metal (M2) A laminate having a region containing a complex oxide , or a gas barrier layer containing a complex oxide of the non-transition metal (M1) and the transition metal (M2), or the complex oxide It is characterized by having a region containing. This feature is a technical feature common to the inventions according to each claim.

As an embodiment of the present invention, from the viewpoint of exhibiting the effects of the present invention, the non-transition metal (M1) is formed in a part of the laminate of the first gas barrier layer and the second gas barrier layer in the thickness direction. Also, it is necessary that a region containing the complex oxide of the transition metal (M2) is present from the viewpoint of forming a sealing layer having a high gas barrier property .

Further, when the non-transition metal is M1, the transition metal is M2, the oxygen is O, and the nitrogen is N, the gas barrier layer or region containing the complex oxide is (M1)(M2) _x O _y N It is preferable that the composite oxide represented by _z is contained and the composition of the composite oxide satisfies the relational expression (1) from the viewpoint that a high-density structure of the metal compound is formed in the region. Is. The relational expression (1) represents that the region containing the complex oxide has a composition lacking oxygen with respect to the stoichiometric composition.

In addition, it is preferable that the layer containing the non-transition metal (M1) is a layer containing polysilazane or a modified product of polysilazane from the viewpoint of uniformly sealing the functional element, and the transition metal ( It is preferable that M2) is selected from niobium (Nb), tantalum (Ta), and vanadium (V) from the viewpoint of forming the composite oxide and further improving the gas barrier property.

Further, at least one organic polymer layer on the substrate and the organic functional layer, a laminate of the first gas barrier layer and the second gas barrier layer, or a gas barrier layer containing the composite oxide, Or, the area and the layer are laminated to improve the adhesion between the base material and the gas barrier layer, the organic functional layer and the gas barrier layer, and the mechanical or thermal stress to the gas barrier layer due to changes in the use environment may This is a preferred embodiment from the viewpoint of preventing damage and defects in the layer and suppressing deterioration of the gas barrier property.

Further, it is a preferred embodiment of the electronic device in the present invention that the functional element has a pair of electrodes and an organic functional layer including at least one light emitting layer between the electrodes.

The method for sealing an electronic device of the present invention is a method for sealing an electronic device in which a functional element and a sealing layer for sealing the functional element are formed on a base material, and as the sealing layer, at least A first gas barrier layer containing a layer 12 to 14 group non-transition metal (M1) oxide and a transition metal (M2) oxide disposed in contact with the first gas barrier layer. A region that is a laminate of the second gas barrier layer to be contained, and that contains a composite oxide of the non-transition metal (M1) and the transition metal (M2) in a part of the thickness of the laminate. there either stack present, or the non-transition metal (M1) and one gas-barrier layer containing a composite oxide of the transition metal (M2), or the region containing the composite oxide, vapor deposition Alternatively, it is formed by a coating method.

As the sealing layer, forming a first gas barrier layer containing the oxide of the non-transition metal (M1) on the functional element side is a gas barrier layer containing the composite oxide, or It is preferable from the viewpoint of efficiently forming the region.

In addition, a second gas barrier layer containing an oxide of the transition metal (M2) is formed on the first gas barrier layer containing an oxide of the non-transition metal (M1) by a vapor phase film forming method. Is preferable from the viewpoint of forming the gas barrier layer or region containing the complex oxide with good productivity and efficiency.

Further, the first gas barrier layer containing an oxide of the non-transition metal (M1) contains polysilazane and a modified polysilazane, and the modified polysilazane is applied with a coating solution containing polysilazane. Then, it can be formed by irradiating with vacuum ultraviolet light to form a gas barrier layer containing the complex oxide, or a region with high accuracy and stability, and to provide a gas barrier property excellent in optical characteristics such as transmittance. This is a preferred embodiment from the viewpoint of obtaining a high sealing layer.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used by the meaning including the numerical value described before and after that as a lower limit and an upper limit.

<<Outline of Electronic Device of the Present Invention>>
The electronic device of the present invention is an electronic device including a pair of electrodes on a base material, an organic functional layer including at least one light emitting layer between the electrodes, and a sealing layer disposed on the organic functional layer. Then, the sealing layer includes a first gas barrier layer containing an oxide of a non-transition metal (M1) of Group 12 to 14 and a transition metal (which is disposed in contact with the first gas barrier layer). laminate der of the second gas barrier layer containing an oxide of M2) is, and the portion of the thickness direction of the laminate, the non-transition metal (M1) and the transition metal (M2) A laminate having a region containing a complex oxide , or a gas barrier layer containing a complex oxide of the non-transition metal (M1) and the transition metal (M2), or the complex oxide It is characterized by having a region containing.

In the present application, the “sealing layer” may be referred to as a “gas barrier layer”, but in that case, the layers are substantially the same.

The functional element according to the present invention is not particularly limited, but preferably refers to an organic EL element, an organic thin film solar cell, a liquid crystal display device, an element made of an organic material such as a touch panel, and particularly to the present invention. The functional element is preferably an organic EL element.

An organic EL element, which is a preferred example of the functional element according to the present invention, is preferably composed of a pair of electrodes and an organic functional layer having at least one light emitting layer between the electrodes. The gas barrier property of the sealing layer that seals the organic EL element is 10 ⁻⁵ to 10 ⁻⁶ g/in terms of water vapor transmission rate (WVTR) under an environment of 25±0.5° C. and 90±2% RH. A very high gas barrier property of m ² ·24h level is required.

The present invention provides the above high gas barrier properties with a first gas barrier layer containing an oxide of a non-transition metal (M1) of Group 12 to 14 and a transition arranged in contact with the first gas barrier layer. It is a laminate of a second gas barrier layer containing an oxide of a metal (M2) , and the non-transition metal (M1) and the transition metal (M2) are provided in a part of the laminate in the thickness direction. of the laminate or region containing composite oxide is present, or the non-transition metal (M1) and said composite oxide gas barrier layer or containing a transition metal (M2), or containing the composite oxide It is realized by a sealing layer having a region.

In addition, the "non-transition metal (M1)" in the present invention means a metal other than a transition metal and belonging to Groups 12 to 14 of the long periodic table, and is referred to as "transition metal (M2)". Means a metal belonging to Groups 3 to 11.

FIG. 1 is a schematic sectional view showing an electronic device including a sealing layer according to an embodiment of the present invention.

In the electronic device 10 shown in FIG. 1A, a pair of electrodes 2 and an organic functional layer 3 having at least one light emitting layer between the electrodes 2 are formed as a functional element on a base material 1. In addition to the configuration in which the organic functional layer 3 is arranged on one surface of the base material, the electrodes 2 and the organic functional layer 3 may be formed on both surfaces of the base material. A sealing layer 4 is formed on the organic functional layer 3 so as to cover the organic functional layer 3 and a part of the base material 1. The sealing layer 4 has a first gas barrier layer 5 containing a non-transition metal (M1) oxide and a second gas barrier layer 6 containing a transition metal (M2) oxide. At the interface between the barrier layer 5 and the gas barrier layer 6, there is a region 7A containing composite oxide of non-transition metal (M1) and transition metal (M2) (hereinafter, also referred to as composite composition region). In FIG. 1A, the sealing layer 4 shows a three-layer structure of the gas barrier layer 5, the gas barrier layer 6 and the region 7A, but it may further have a plurality of regions 7A which are composite composition regions. The layer order of the first gas barrier layer 5 and the second gas barrier layer 6 may be in any order.

In the electronic device 10 shown in FIG. 1B, a pair of electrodes 2 and an organic functional layer 3 having at least one light emitting layer between the electrodes are formed on a substrate 1, and the non-transition metal ( It has a gas barrier layer 7B (also referred to as a composite composition gas barrier layer in the present application) composed of a composite oxide of M1) and the transition metal (M2). The gas barrier layer 7B shown here is co-deposited to be described later and simultaneously sputters an oxide of a non-transition metal (M1) and an oxide of the transition metal (M2) as sputtering targets, and introduces oxygen as a reactive gas. Then, when forming the composite oxide of the non-transition metal (M1) and the transition metal (M2), the gas barrier layer is formed under the condition that oxygen is less than the stoichiometric composition.

The electronic device 10 shown in FIG. 1C has at least one surface of the base material, preferably both surfaces, when the base material 1 is a water-permeable base material such as a resin film in the configuration of the electronic device shown in FIG. 1A. The embodiment having the gas barrier layer 8 is shown in FIG.

FIG. 2 is a schematic sectional view showing an electronic device including an organic polymer layer and a sealing layer according to another embodiment of the present invention.

The electronic device 10 shown in FIG. 2A is formed by forming a pair of electrodes 2 on a base material 1 and an organic functional layer 3 having at least one light emitting layer between the electrodes, and on the organic functional layer 3, In this mode, the organic polymer layer 9 is formed so as to cover the entire organic functional layer 3 and a part of the base material 1, and then the organic polymer layer 9 is sealed by the sealing layer 4. The sealing layer 4 has a first gas barrier layer 5 containing an oxide of a non-transition metal (M1) and a second gas barrier layer 6 containing an oxide of a transition metal (M2). A region 7A (composite composition region) containing a composite oxide of a non-transition metal (M1) and a transition metal (M2) exists at the interface between the layer 5 and the layer 6.

In FIG. 2A, the organic polymer layer 9 and the sealing layer 4 are further laminated as an upper layer.

In the electronic device 10 shown in FIG. 2B, the sealing layer 4 has a gas barrier layer 7B (composite composition gas barrier layer) composed of a composite oxide of the non-transition metal (M1) and the transition metal (M2). This is an embodiment, and similarly, the organic polymer layer 9 and the sealing layer 4 are laminated and formed.

Although not shown, other functional layers or intermediate layers are appropriately provided between the base material and the organic functional layer, between the organic functional layer and the sealing layer, and on the other surface of the base material. It may be formed.

[Composite composition area]
The “region 7A containing the composite oxide of the non-transition metal (M1) and the transition metal (M2)” according to the present invention will be described below as a “composite composition region”.

In the "composite composition region" of the present invention, the content of composition and the layer thickness can be determined by the following composition analysis by XPS.

<Composition analysis by XPS and measurement of thickness of composite composition region>
The composite composition region in the present invention means the first gas barrier layer containing the oxide of the non-transition metal (M1) and the transition metal (when the composition distribution in the thickness direction of the sealing layer is analyzed by the XPS method. The non-transition metal (M1) and the transition metal (M2) coexist in the interface region with the second gas barrier layer containing the oxide of M2), and the transition metal (M2)/non-transition metal ( The value of the atomic ratio of M1) is within the range of 0.02 to 49, and is defined as a region having a thickness of 5 nm or more.

The method of measuring the composite composition region by the XPS analysis method will be described below.

The element concentration distribution (hereinafter referred to as depth profile) in the thickness direction of the sealing layer according to the present invention is specifically a non-transition metal (M1) distribution curve (for example, a silicon distribution curve), a transition metal (M2) ) A distribution curve (for example, a niobium distribution curve), oxygen (O), nitrogen (N), carbon (C) distribution curve, etc. are measured by X-ray photoelectron spectroscopy (XPS: Xray Photoelectron Spectroscopy) and a rare gas such as argon. By using together with ion sputtering, it can be created by so-called XPS depth profile measurement, in which the surface composition is sequentially analyzed while exposing the inside from the surface of the sealing layer. The distribution curve obtained by such XPS depth profile measurement can be created, for example, with the ordinate representing the atomic ratio of each element (unit: atom %) and the abscissa representing the etching time (sputtering time). Incidentally, in the distribution curve of the element with the horizontal axis as the etching time in this way, since the etching time is roughly correlated with the distance from the surface of the sealing layer in the thickness direction of the sealing layer in the layer thickness direction, The "distance from the surface of the sealing layer in the thickness direction of the sealing layer" is defined as the distance from the surface of the sealing layer calculated from the relationship between the etching rate and the etching time used when measuring the XPS depth profile. Can be adopted. In addition, as a sputtering method used in such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is used, and the etching rate (etching rate) is 0.05 nm/ sec (SiO ₂ thermal oxide film conversion value) is preferable.

An example of specific conditions of XPS analysis applicable to the present invention will be shown below.

・Analyzer: QUANTERA SXM made by ULVAC-PHI
・X-ray source: Monochromatic Al-Kα
・Sputtering ion: Ar (2 keV)
Depth profile: The depth profile in the depth direction is obtained by repeating the measurement at a predetermined thickness interval with a sputtering thickness converted to SiO ₂ . This thickness interval was set to 1 nm (data for each 1 nm is obtained in the depth direction).

-Quantification: The background was determined by the Shirley method, and the peak area was quantified using the relative sensitivity coefficient method. For data processing, MultiPak manufactured by ULVAC-PHI, Inc. is used. 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).

The composition ratio is calculated from the obtained data, the non-transition metal M1 and the transition metal M2 coexist, and the value of the atomic number ratio of transition metal M2/non-transition metal M1 is 0.02 to 49. The range was determined, this was defined as the composite composition region, and its thickness was determined. The thickness of the composite composition region represents the sputtering depth in XPS analysis in terms of SiO ₂ .

In the present invention, when the thickness of the composite composition region is 5 nm or more, it is determined as “composite composition region”. From the viewpoint of gas barrier property, there is no upper limit of the thickness of the composite composition region, but from the viewpoint of optical characteristics and the productivity, it is preferably in the range of 5 to 200 nm, more preferably 8 to 100 nm. It is within the range, and more preferably within the range of 10 to 60 nm.

FIG. 3 shows a schematic graph of an element profile when the composition distribution of the non-transition metal M1 and the transition metal M2 in the thickness direction of the sealing layer including the composite composition region is analyzed by the XPS method.

In FIG. 3, elemental analysis of M1, M2, O, N, and C is performed in the depth direction from the surface of the sealing layer (the left end of the graph), and the abscissa indicates the depth of sputtering (film thickness: nm). 3 is a graph showing the content rates (atom %) of M1 and M2 on the vertical axis.

In FIG. 3, from the left, the elemental composition of the second gas barrier layer containing the oxide of the transition metal (M2), the elemental composition of the composite composition region, and the elemental composition of the non-transition metal (M1: Si in the figure) The elemental composition profile in 1 gas barrier layer is shown, and the value of the atomic number ratio of M2/M1 is within the range of 0.02-49, and a composite composition area|region is an area|region with a thickness of 5 nm or more.

<Structure of electronic device of the present invention>
[1] Substrate As the substrate according to the present invention, specifically, glass or a resin film is preferably applied, and when flexibility is required, a resin film is preferable.

Preferred resins include polyester resins, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluororesins, polyimides, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, cellulose acylate resins. , Polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, fluorene ring modified Examples include base materials containing thermoplastic resins such as polyester resins and acryloyl compounds. The resin may be used alone or in combination of two or more kinds.

The base material is preferably made of a heat resistant material. Specifically, a substrate having a linear expansion coefficient of 15 ppm/K or more and 100 ppm/K or less and a glass transition temperature (Tg) of 100° C. or more and 300° C. or less is used. The base material meets the requirements for a laminated film for electronic parts and displays. That is, when the sealing layer according to the present invention is used for these purposes, the base material may be exposed to a step of 150°C or higher. In this case, if the linear expansion coefficient of the base material exceeds 100 ppm/K, the dimensions of the substrate will not be stable when flowing through the above-mentioned temperature step, and the barrier performance will deteriorate due to thermal expansion and contraction. Or, a problem that the heat process cannot be endured easily occurs. If it is less than 15 ppm/K, the film may be broken like glass and flexibility may be deteriorated.

The Tg and the coefficient of linear expansion of the base material can be adjusted by additives and the like. More preferable specific examples of the thermoplastic resin that can be used as the base material include, for example, polyethylene terephthalate (PET: 70° C.), polyethylene naphthalate (PEN: 120° C.), polycarbonate (PC: 140° C.), alicyclic Polyolefin (for example, Zeonor (registered trademark) 1600:160° C. manufactured by Nippon Zeon Co., Ltd.), 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: JP 2000-227603 compound: 225° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205° C.), acryloyl compound (JP 2002-80616 A). Compounds described: 300°C or higher) and the like (Tg is shown in parentheses).

Since the electronic device of the present invention is suitable for an electronic device such as an organic EL element, the base material is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105:1981, that is, using an integrating sphere type light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

Further, the above-mentioned base material may be an unstretched film or a stretched film. The base material can be manufactured by a conventionally known general method. As for the method for producing these base materials, the matters described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately adopted.

The surface of the substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and may be performed by combining the above treatments as necessary. May be. Further, the substrate may be subjected to easy adhesion treatment.

The base material may be a single layer or a laminated structure of two or more layers. When the base material has a laminated structure of two or more layers, the base materials may be of the same type or of different types.

The thickness of the substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 μm, more preferably 20 to 150 μm.

In the case of a resin film, a resin film substrate with a gas barrier layer is preferable (Fig. 1C).

The gas barrier layer may have an inorganic film, an organic film, or a hybrid film of both of them formed on the surface of the film substrate, and is measured by a method according to JIS K 7129-1992, 25±0. A gas barrier film having a water vapor permeability of 0.01 g/m ² ·24 h or less under an environment of 0.5° C. and 90±2% RH is preferable, and further, a method according to JIS K 7126-2006. The measured oxygen permeability under an environment of 85° C. and 85% RH is 1×10 ⁻³ mL/m ² ·24 h·atm or less, and water vapor permeability is 1×10 ⁻³ g/m ² ·24 h. The following high gas barrier film is preferred.

As a material for forming the gas barrier layer, any material may be used as long as it has a function of suppressing entry of substances such as moisture and oxygen that cause deterioration of the element, and for example, silicon oxide, silicon dioxide, silicon nitride or the like can be used. .. Furthermore, in order to improve the brittleness of the layer, it is more preferable to have a laminated structure of these inorganic layers and a layer made of an organic material. The order of laminating the inorganic layer and the organic layer is not particularly limited, but it is preferable to alternately laminate the both layers a plurality of times.

The gas barrier layer is not particularly limited. For example, in the case of an inorganic gas barrier layer such as silicon oxide, silicon dioxide or silicon nitride, an inorganic material is sputtered (for example, magnetron cathode sputtering, flat plate magnetron sputtering, two-pole AC). Reactive sputtering methods such as flat plate magnetron sputtering, 2-pole AC rotary magnetron sputtering, etc. are included), evaporation methods (eg, resistance heating evaporation, electron beam evaporation, ion beam evaporation, plasma assisted evaporation, etc.), thermal CVD method, catalytic chemistry. Layer formation by chemical vapor deposition methods such as vapor phase growth method (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), photo CVD method, plasma CVD method (PE-CVD), epitaxial growth method, atomic layer growth method, etc. Preferably.

Further, a method of forming an inorganic gas barrier layer by applying a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) on a support, and then performing a modification treatment by irradiation with vacuum ultraviolet light or the like. The inorganic gas barrier layer can also be formed by a film metallization technique such as metal plating on a resin base material or bonding a metal foil and a resin base material.

Further, the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.

The organic layer is formed, for example, by coating an organic monomer or organic oligomer on a resin substrate to form a layer, which is subsequently polymerized using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device. And, it can be formed by crosslinking if necessary. It can also be formed, for example, by depositing an organic monomer or organic oligomer capable of flash evaporation and radiation crosslinking and then forming a polymer from the organic monomer or oligomer. Coating efficiency can be improved by cooling the resin substrate.

Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating). In addition, examples of the laminate of the inorganic layer and the organic layer include the laminates described in International Publication No. 2012/003198 and International Publication No. 2011/013341.

In the case of a laminated body of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The layer thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm. The layer thickness of the organic layer is preferably in the range of 100 nm to 100 μm, more preferably in the range of 1 to 50 μm.

[2] Organic functional layer The sealing layer according to the present invention can be preferably applied to a functional element whose performance is deteriorated by chemical components in the air (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.).

Examples of the functional element according to the present invention include organic EL elements, liquid crystal display elements (LCD), thin film transistors, touch panels, electronic paper, solar cells (PV), and the like. From the viewpoint that the effect of the present invention can be obtained more efficiently, an organic EL element or a solar cell is preferable, and an organic EL element is particularly preferable.

The functional element is preferably an organic functional layer having a pair of electrodes on a base material and at least one light emitting layer between the electrodes, and constitutes an organic EL element.

[2.1] Organic EL element An organic EL element comprising a pair of electrodes according to the present invention and an organic functional layer having at least one light emitting layer between the electrodes is, for example, a transparent substrate, an anode, a One organic functional layer group, a light emitting layer, a second organic functional layer group, and a cathode are laminated. The first organic functional layer group includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, and the like, and the second organic functional layer group includes, for example, a hole blocking layer, an electric transport layer, an electron injection layer. Etc. The first organic functional layer group and the second organic functional layer group may each be composed of only one layer, or the first organic functional layer group and the second organic functional layer group may not be provided.

Below, the typical example of a structure of an organic EL element is shown.

(I) Anode/hole injecting/transporting layer/light emitting layer/electron injecting/transporting layer/cathode (ii) Anode/hole injecting/transporting layer/light emitting layer/hole blocking layer/electron injecting/transporting layer/cathode (iii) anode/ Hole injecting/transporting layer/electron blocking layer/light emitting layer/hole blocking layer/electron injecting/transporting layer/cathode (iv) anode/hole injecting layer/hole transporting layer/light emitting layer/electron transporting layer/electron injecting layer/ Cathode (v) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode (vi) Anode/hole injection layer/hole transport layer/electron blocking Layer/Light emitting layer/Hole blocking layer/Electron transport layer/Electron injection layer/Cathode Furthermore, the organic EL device may have a non-light emitting intermediate layer. The intermediate layer may be a charge generation layer or a multi-photon unit structure.

For an outline of the organic EL element applicable to the present invention, see, for example, JP 2013-157A.
634, JP 2013-168552, JP 2013-177361, JP 2013-187211, JP 2013-191644, JP 2013-191804, JP 2013-225678. JP, 2013-235994, JP 2013-243234, JP 2013-243236, JP 2013-242366, JP 2013-243371, JP 2013-245179, The configurations described in JP-A-2014-003249, JP-A-2014-003299, JP-A-2014-013910, JP-A-2014-017493, JP-A-2014-017494, etc. may be mentioned. it can.

[3] Sealing Layer [3.1] Outline of Sealing Layer and Composite Composition Region The sealing layer according to the present invention is a layer that exhibits gas barrier properties, and the functional element according to the present invention is used as a base material. And a first gas barrier layer containing an oxide of a non-transition metal (M1) selected from metals of Groups 12 to 14 of the long periodic table, and a transition layer which is sandwiched and sealed together. Ri laminate der of the second gas barrier layer containing an oxide of the metal (M2), and a part of the thickness direction of the laminate, the non-transition metal (M1) and the transition metal (M2 or regions containing complex oxide is a laminate exists), or the or a gas barrier layer containing a composite oxide of non-transition metals (M1) and transition metal (M2), or the complex It is a region containing an oxide.

The gas barrier property of the sealing layer has an oxygen permeability of 1×10 ⁻ , which is measured by a method according to JIS K 7126-2006 when calculated with a laminate in which the sealing layer is formed on a substrate. Water vapor permeability under an environment of 25±0.5° C. and 90±2% RH, which is ³ mL/m ² ·24 h·atm or less and is measured by a method according to JIS K 7129-1992, is 1×10. A high gas barrier property of ⁻³ g/m ² ·24 h or less is preferable, and 1×10 ⁻⁵ g/m ² ·24 h or less is particularly preferable.

In the case of a laminated body of a first gas barrier layer and a second gas barrier layer, an oxide and a transition metal (M2) of a non-transition metal (M1) selected from the metals of Groups 12 to 14 above. The oxygen deficient region of the oxide of No. 2 is continuously present in the thickness direction of the sealing layer in a thickness of a predetermined value or more (specifically, 5 nm or more) (this is referred to as “composite composition region” in the present specification). It is expressed as “.”). Although the details of this feature will be described later, as long as this feature is satisfied, regions other than the composite composition region of the encapsulation layer are, for example, non-transition metal (M1) oxides and transition metals (M1) that do not correspond to the composite composition region ( It may be a layer of an oxide of M2) (which may be an oxygen-deficient region or a stoichiometric composition region).

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

The transition metal (M2) is not particularly limited, and any transition metal may be used alone or in combination. Here, the transition metal refers to the elements of Group 3 to Group 11 of the long periodic table, and the transition metals include 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 are mentioned as the transition metal (M2) which can obtain a good gas barrier property. Among these, from the results of various investigations, it is considered that Nb, Ta, and V, which are Group 5 elements, are particularly likely to bond to the non-transition metal (M1) contained in the sealing layer, and thus are preferably used. be able to.

In particular, when the transition metal (M2) is a Group 5 element (particularly Nb) and the non-transition metal (M1) is Si, a remarkable effect of improving the gas barrier property is obtained. It is considered that this is because the bond between Si and the Group 5 element (in particular, Nb) is likely to occur. Further, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb or Ta, which is a compound having good transparency.

The gas barrier layer used for the sealing layer is formed by sputtering an inorganic material containing a non-transition metal (M1) or a transition metal (M2) (for example, magnetron cathode sputtering, flat plate magnetron sputtering, 2-pole AC flat plate magnetron sputtering). (Including reactive sputtering methods such as 2-pole AC rotary magnetron sputtering), vapor deposition methods (eg, resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition), thermal CVD methods, catalytic chemical vapor deposition methods. (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), optical CVD method, plasma CVD method (PE-CVD), epitaxial growth method, atomic layer growth method, or other vapor phase film forming method or the like. You can In the present invention, the sputtering method or the vapor deposition method is preferably used, and the sputtering method is particularly preferably used.

Further, as a method for forming the gas barrier layer containing the composite oxide of the non-transition metal (M1) and the transition metal (M2), it is preferable to use a known co-evaporation method. As such a co-deposition method, a co-sputtering method is preferably mentioned. The co-sputtering method adopted in the present invention is, for example, a composite target composed of an alloy containing both non-transition metal (M1) and transition metal (M2), or a composite oxide of metal (M1) and transition metal (M2). It may be a single-source sputtering using a composite target consisting of Further, the co-sputtering method in the present invention may be multi-source simultaneous sputtering using a plurality of sputtering targets containing a simple substance of metal (M1) or its oxide and a simple substance of transition metal (M2) or its oxide. Good. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a composite oxide using these sputtering targets, for example, JP-A-2000-160331, JP-A-2004-068109, and JP-A-2004-068109 are disclosed. Reference may be made to the description in the publication such as 2013-043761. The film forming conditions for carrying out the co-evaporation method are as follows: the ratio of the transition metal (M2) to oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, the film forming time The gas supply amount, the degree of vacuum during film formation, and one or more conditions selected from the group consisting of electric power during film formation are exemplified, and these film formation conditions (preferably oxygen content) are selected. By adjusting the pressure, it is possible to form a thin film of a composite oxide having an oxygen deficiency composition. 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 made into the composite composition region. Therefore, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the composite composition region. In addition, in order to control the thickness of the composite composition region, for example, the film formation time when performing the co-evaporation method may be adjusted.

[Oxygen deficiency region]
In the sealing layer according to the present invention, the composition of the compound in the composite composition region of the sealing layer is (M1)(M2) _x O _y , where M1 is the non-transition metal, M2 is the transition metal, O is oxygen, and N is nitrogen. When N _z , the following relational expression (1) is preferably satisfied.

(1) (2y+3z)/(a+bx)<1.0
(However, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, 0.02≦x≦49, 0<y, 0≦z, a : Represents the maximum valence of M1, b: represents the maximum valence of M2.)
The above relational expression (1) represents that the composite composition region of the sealing layer contains the oxygen deficiency composition of the composite oxide of the non-transition metal (M1) and the transition metal (M2).

As described above, the composition of the composite oxide of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1)(M2) _x O _y N _z . As is clear from this composition, the composite oxide may partially include a nitride structure. Here, the maximum valence of the 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 complex oxide (including a part of the nitride) has a stoichiometric composition, (2y+3z)/(a+bx)=1.0. This formula means that the total number of bonds of the non-transition metal (M1) and the transition metal (M2) and the total number of bonds of O and N are the same, and in this case, the non-transition metal (M1) Thus, both the transition metal (M2) and O or N are bonded. In addition, in this invention, when two or more types are used together as a non-transition metal (M1), or when two or more types are used together as a transition metal (M2), the maximum valence of each element is set to The composite valence calculated by weighted averaging according to the abundance ratio is adopted as the values of a and b of the “maximum valence”.

On the other hand, in the case of (2y+3z)/(a+bx)<1.0 as in the composite composition region according to the present invention, with respect to the total bond of the non-transition metal (M1) and the transition metal (M2). , O, N means that the total number of bonding hands is insufficient, and this state is the “oxygen deficiency” of the composite oxide. In the oxygen-deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have a possibility of bonding with each other, and the non-transition metal (M1) and the transition metal (M2) are bound to each other. It is considered that when is directly bonded, a denser and denser structure is formed than in the case where O and N are bonded between metals, and as a result, the gas barrier property is improved.

In the present invention, the composite composition region is a region where the value of x satisfies 0.02≦x≦49 (0<y, 0≦z). This is defined as a region in which the value of the atomic number ratio of transition metal (M2)/non-transition metal (M1) is within the range of 0.02 to 49 and the thickness is 5 nm or more. It has the same definition as what was done. In this region, both the non-transition metal (M1) and the transition metal (M2) participate in the direct bonding of the metals, so that the composite composition region satisfying this condition exists with a thickness of a predetermined value or more (5 nm). Therefore, it is considered that it contributes to the improvement of the gas barrier property. It is considered that the closer the abundance ratios of the non-transition metal (M1) and the transition metal (M2) are, the more it can contribute to the improvement of the gas barrier property. Therefore, the composite composition region is a region satisfying 0.1≦x≦10. Is preferably included in a thickness of 5 nm or more, a region satisfying 0.2≦x≦5 is more preferably included in a thickness of 5 nm or more, and a region satisfying 0.3≦x≦4 is included in a thickness of 5 nm or more. It is more preferable to include

Here, as described above, it was confirmed that if the composite composition region satisfying (2y+3z)/(a+bx)<1.0 is present, the effect of improving the gas barrier property is exhibited. , (2y+3z)/(a+bx)≦0.9 is preferable, (2y+3z)/(a+bx)≦0.85 is more preferable, and (2y+3z)/(a+bx)≦0.8 is satisfied. Is more preferable. Here, the smaller the value of (2y+3z)/(a+bx) in the composite composition region, the higher the effect of improving the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a sealing 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 further preferable.

In the present invention, the thickness of the composite composition region in which good gas barrier properties are obtained is 5 nm or more in terms of SiO ₂ equivalent sputtering thickness, and this thickness is preferably 8 nm or more, and 10 nm or more. Is more preferable, and 20 nm or more is further preferable.

The encapsulating layer having the above-described structure exhibits a very high gas barrier property that can be used as an encapsulating layer for electronic devices such as organic EL elements.

Here, as a result of various studies by the present inventor, the oxygen deficient composition film of the compound (oxide) of the non-transition metal (M1) was used alone to form the sealing layer, and the transition metal (M2) was formed. When a sealing layer was formed by using an oxygen-deficient composition film of a compound (oxide) alone, it was observed that the gas barrier property improved as the degree of oxygen deficiency increased, but the gas barrier property It didn't improve. In response to this result, the layer containing the oxide of the non-transition metal (M1) and the layer containing the oxide of the transition metal (M2) are stacked, and the non-transition metal (M1) and the transition metal (M2) are separated from each other. It has been found that when a composite composition region existing at the same time is formed and the composite composition region is made to have an oxygen deficiency composition, the gas barrier property is further improved as the degree of oxygen deficiency increases.

This is because, as described above, 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) and the bond between the transition metals (M2). Then, it is considered that the high density structure of the composite metal oxide is formed in the composite composition region by making the composite composition region an oxygen deficient composition.

Here, in the layered structure of the layer containing the oxide of the non-transition metal (M1) and the layer containing the oxide of the transition metal (M2) as described above, the composite composition region composed of the composite oxide is present at the stacking interface. Is formed. However, the abundance ratio of each metal element (M1 or M2) to the metal elements contained in the composite composition region is formed with a certain large inclination with respect to the thickness direction of the composite composition region. As a result, the oxygen-deficient composition of the composite oxide of the non-transition metal (M1) and the transition metal (M2) is formed in the above-mentioned composite composition region, but the thickness thereof is about 20 nm at the maximum, which is limited. Will be things.

In particular, the thickness of the region where (M1)/{(M1)+(M2)} is within the range of 0.1 to 0.9, which has a high effect of improving the gas barrier property, is formed only up to about 10 nm. The gas barrier properties that can be achieved by the above laminated structure are limited, and even if the layer thickness of each layer in the above laminated structure is increased, there is almost no change in the above thickness.

Based on the above-mentioned findings, the present inventors have found that 0.02≦x≦, which is a preferable condition for both the non-transition metal (M1) and the transition metal (M2) described above to participate in the direct bond between metals. By changing the thickness of the oxygen deficient composition of the composite oxide of non-transition metal (M1) and transition metal (M2) satisfying 49, the study on the critical thickness at which the effect of improving the gas barrier property can be seen is advanced. It was As a result, as described above, it was confirmed that if the thickness is 5 nm or more, a very remarkable effect of improving the gas barrier property is observed, and the present invention has been completed.

[3.2] Method for Forming Sealing Layer The method for sealing an electronic device according to the present invention is a first gas barrier layer containing at least one oxide of a non-transition metal of group 12 to 14 (M1). And a second gas barrier layer laminate containing an oxide of a transition metal (M2) arranged in contact with the first gas barrier layer , and a part of the laminate in the thickness direction. A laminate having a region containing a complex oxide of the non-transition metal (M1) and the transition metal (M2), or a complex oxide of the non-transition metal (M1) and the transition metal (M2). The electronic device is characterized in that the electronic device is sealed by a gas barrier layer containing the compound oxide or a region containing the composite oxide by a sealing layer formed by a vapor deposition method or a coating method.

As the sealing layer, it is preferable to form a first gas barrier layer containing the oxide of the non-transition metal (M1) on the functional element side, and containing the oxide of the transition metal (M2). It is preferable that the second gas barrier layer is formed on the first gas barrier layer containing the non-transition metal (M1) oxide by a vapor deposition method.

Further, the first gas barrier layer containing the oxide of the non-transition metal (M1) contains polysilazane and a modified polysilazane, and the modified polysilazane is applied with a coating solution containing polysilazane. Then, it is preferably formed by irradiating with vacuum ultraviolet light.

[3.2.1] Formation of first gas barrier layer containing oxide of non-transition metal (M1) and second gas barrier layer containing oxide of transition metal (M2) First gas barrier Formation of the layer containing the oxide of the non-transition metal (M1) which is a layer and the layer containing the oxide of the transition metal (M2) which is the second gas barrier layer is not particularly limited. It is preferable to use a conventionally known vapor-phase film forming method using an existing thin film deposition technique from the viewpoint of efficiently forming a composite composition region.

These vapor phase film forming methods can be used by known methods. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering method, vapor deposition method, ion plating method, ion assisted vapor deposition method, plasma CVD (chemical vapor deposition) method, and ALD method. A chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method may be used. Among them, it is preferable to form the film by the physical vapor deposition (PVD) method because it enables film formation without damaging the organic functional layer and has high productivity, and it is more preferable to form the film by the sputtering method. preferable.

For the film formation by the sputtering method, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering and 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.

Further, a reactive sputtering method using a transition mode which is intermediate between the metal mode and the oxide mode can be used. By controlling the sputtering phenomenon so that the transition region is formed, it is possible to form a metal oxide film at a high film formation speed, which is preferable. As the inert gas used as the process gas, He, Ne, Ar, Kr, Xe or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a thin film of a composite oxide of non-transition metal (M1) and transition metal (M2), nitriding oxide, oxycarbide, etc. is formed. be able to. The film forming 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, film material, layer thickness and the like.

The layer thickness of the first gas barrier layer and the second gas barrier layer is preferably in the range of 1 to 500 nm, more preferably 10 to 300 nm.

[3.2.2] Formation of gas barrier layer containing complex oxide of non-transition metal (M1) and transition metal (M2) Complex oxide of non-transition metal (M1) and transition metal (M2) The contained gas barrier layer can be formed by adopting a co-evaporation method using a non-transition metal (M1) oxide and the above transition metal (M2) oxide as sputtering targets.

The film forming conditions for carrying out the co-evaporation method include the ratio of the non-transition metal (M1) and the transition metal (M2) to oxygen in the film forming raw material, the inert gas and the reactive gas at the time of film formation. One or two or more conditions selected from the group consisting of a ratio, a gas supply amount during film formation, a vacuum degree during film formation, and an electric power during film formation are exemplified, and these film formation conditions ( Preferably, by adjusting the oxygen partial pressure), a thin film composed of a complex oxide having an oxygen deficiency composition can be formed. That is, by forming the sealing layer using the co-evaporation method as described above, most of the region in the thickness direction of the formed sealing layer can be made into the composite composition region. Therefore, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the composite composition region. In addition, in order to control the thickness of the composite composition region, for example, the film formation time when performing the co-evaporation method may be adjusted.

For details of the co-evaporation method, a method for producing a sputtering target and a method for producing a thin film made of a complex oxide using these sputtering targets are described in, for example, JP-A-2000-160331 and JP-A-2004-2004. Reference can be made as appropriate to the descriptions in 068109, JP2013-047361A, and the like.

[3.2.3] Formation of layer containing polysilazane or modified polysilazane as non-transition metal (M1) The layer containing non-transition metal (M1) according to the present invention contains Si as described above. It is more preferable, and Si alone is particularly preferable.

In that case, the layer containing the non-transition metal (M1) is also preferably a layer containing polysilazane or a modified product of polysilazane, and the modified polysilazane is used as a coating solution containing polysilazane according to the present invention. It is preferable that it is a layer formed by coating on the functional element according to, and irradiating with vacuum ultraviolet light, since a sealing layer having high gas barrier properties excellent in optical characteristics such as transmittance can be obtained. .. The number of layers formed is not particularly limited and may be at least one layer, and may be a plurality of layers.

The modification treatment is preferably a vacuum ultraviolet light irradiation treatment. The sealing layer exhibits a gas barrier property by a modification treatment such as irradiation with vacuum ultraviolet light.

Here, first, an example of a method for forming a layer containing a non-transition metal (M1) will be described, taking a case where the silicon compound is polysilazane as an example.

A coating solution containing polysilazane can be applied by a known wet coating method to perform a modification treatment, and a layer which will be a part of the sealing layer can be formed.

The "polysilazane" used in the present invention is a polymer having a silicon-nitrogen bond in its structure, which is a precursor of silicon oxynitride, and a polymer having the structure of the following general formula (1) is preferably used. ..

式中、Ｒ^１、Ｒ^２、及びＲ^３は、各々水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルキルシリル基、アルキルアミノ基、又はアルコキシ基を表す。

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

In the present invention, perhydropolysilazane in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferable from the viewpoint of the denseness of the resulting sealing layer film.

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

In addition, regarding the details of polysilazane, paragraphs “0024” to “0040” in JP 2013-255910 A, paragraphs “0037” to “0043” in JP 2013-188942 A, and JP 2013-2013 A that are conventionally known. Paragraphs "0014" to "0021" of Japanese Patent No. 151123, paragraphs "0033" to "0045" of Japanese Patent Laid-Open No. 2013-052569, paragraphs "0062" to "0075" of Japanese Patent Laid-Open No. 2013-129557, 2013 It can be adopted by referring to paragraphs “0037” to “0064” and the like of JP-A-226758.

The application of the coating solution containing polysilazane is performed in a nitrogen atmosphere such as in a glove box in order to suppress deterioration of the electronic device due to oxygen or water vapor. Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane. Specific examples thereof include a spin coating method, a roll coating method, a flow coating method, an inkjet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method and a gravure printing method. After applying the coating solution, it is preferable to dry the coating film. The organic solvent contained in the coating film can be removed by drying the coating film. Regarding the forming method, refer to paragraphs “0058” to “0064” of JP-A-2014-151571 and paragraphs “0052” to “0056” of JP-A-2011-183773 that are conventionally known. You can

The modification treatment means a conversion reaction of polysilazane to silicon oxide or silicon oxynitride. Similarly, the reforming process is performed in a glove box under a nitrogen atmosphere or under reduced pressure.

For the modification treatment in the present invention, a known method based on the conversion reaction of polysilazane can be selected. In the present invention, a conversion reaction using plasma, ozone, or ultraviolet rays, which allows a conversion reaction at a low temperature, is preferable. Conventionally known methods can be used for plasma and ozone. In the present invention, a layer containing a non-transition metal (M1) is formed by providing a coating film of a polysilazane-containing liquid and irradiating it with vacuum ultraviolet light (also referred to as VUV) having a wavelength of 200 nm or less for modification treatment. Preferably.

The layer thickness is preferably in the range of 1 to 500 nm, more preferably 10 to 300 nm. Of the non-transition metal-containing layer, the entire layer may be a modified layer, but the modified modified layer preferably has a thickness of 1 to 50 nm, more preferably 1 to 10 nm.

In the vacuum ultraviolet light irradiation step in the present invention, it is preferable that the illuminance of the vacuum ultraviolet light in the coating film surface for receiving the polysilazane coating film is in the range of 30~200mW / cm ^2, the range of 50~160mW / cm ² Is more preferable. By setting the illuminance of vacuum ultraviolet light to 30 mW/cm ² or more, the reforming efficiency can be sufficiently improved, and at 200 mW/cm ² or less, the occurrence rate of damage to the coating film is extremely suppressed, and the substrate It is preferable because damage to the can be reduced.

In the electronic device of the present invention, from the viewpoint of forming a region containing the composite oxide, it is not necessary to irradiate the polysilazane layer coating film with an excessive amount of vacuum ultraviolet light, and without performing irradiation with vacuum ultraviolet light. However, since a high gas barrier property is obtained, it is possible to reduce damage to the functional element.

When performing irradiation with vacuum ultraviolet light, the irradiation energy amount of vacuum ultraviolet light on the polysilazane layer coating surface is preferably in the range of 0.01 to 0.9 J/cm ² , and 0.05 to 0.5 J. The range of /cm ² is more preferable from the viewpoint of reducing damage to the device.

A rare gas excimer lamp is preferably used as the vacuum ultraviolet light source. Since vacuum ultraviolet light is absorbed by oxygen and the efficiency in the vacuum ultraviolet light irradiation step is likely to decrease, it is preferable to perform vacuum ultraviolet light irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of vacuum ultraviolet light irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, still more preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm. is there.

Heat treatment can also be used for the modification treatment. The heating conditions are preferably in the range of 50 to 300° C., more preferably in the range of 70 to 200° C., preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes. By carrying out dry operation, condensation is performed and a modified product can be formed.

Examples of the heat treatment include a method of heating a coating film by heat conduction by bringing a base material into contact with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, an infrared region such as an IR heater. Examples of the method include the method using light, but the method is not particularly limited. Moreover, you may select suitably the method which can maintain the smoothness of the coating film containing a silicon compound.

The temperature of the coating film during the heat treatment is preferably adjusted appropriately within the range of 50 to 250°C, and more preferably within the range of 50 to 120°C.

The heating time is preferably within the range of 1 second to 10 hours, more preferably within the range of 10 seconds to 1 hour.

In these modification treatments, for example, paragraphs “0055” to “0091” of JP2012-086394A, paragraphs “0049” to “0085” of JP2012-0061154A, and JP2011-251460A. The contents described in paragraphs “0046” to “0074” of the publication can be referred to.

(Additional element)
In the present invention, the coating liquid for forming the layer containing the non-transition metal (M1) has at least an additive element (at least selected from the group consisting of elements of Groups 2 to 14 of the long periodic table). One element) can be included. Examples of additional elements include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), magnesium (Mg). ), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), potassium (K). ), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), germanium (Ge) and the like. ..

The layer containing the non-transition metal (M1) according to the present invention is preferably formed by applying a coating solution containing a polysilazane and an aluminum compound or a polysilazane and a boron compound, and drying the layer.

Examples of the aluminum compound applicable to the present invention include aluminum isopropoxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, and aluminum tri-n-. Butyrate, aluminum trisec-butyrate, aluminum ethylacetoacetate diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropyloxide trimer and the like. be able to.

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

Among these, aluminum compounds are preferable. Specific commercial products include, for example, AMD (aluminum diisopropylate mono sec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate/diisopropylate), ALCH-TR (aluminum trisethylacetate). Acetate), aluminum chelate M (aluminum alkylacetoacetate/diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate/monoacetylacetonate), aluminum chelate A(W) (aluminum trisacetylacetonate) (above, Kawa Ken Fine Chemical Co., Ltd.), Plane Act (registered trademark) AL-M (acetoalkoxy aluminum diisopropylate, manufactured by Ajinomoto Fine Chemical Co., Ltd.) and the like.

When these compounds are used, it is preferable to mix them with a coating solution containing polysilazane under an inert gas atmosphere. This is because these compounds are prevented from reacting with moisture and oxygen in the atmosphere and vigorously oxidizing. When mixing these compounds and polysilazane, it is preferable to raise the temperature to 30 to 100° C. and hold for 1 minute to 24 hours while stirring.

The content of the additional element in the layer containing the non-transition metal (M1) is preferably 0.1 to 20 mol% with respect to the content of silicon (Si) of 100 mol %. , And more preferably 0.5 to 10 mol %.

[3.3] Sealing Method for Electronic Device Using Sealing Layer In order to seal the electronic device by bonding the sealing layer on the base material and the functional element, any curable resin sealant is used. It is preferable to bond with a stop material. For the resin sealing material, a suitable adhesive can be appropriately selected from the viewpoint of improving the adhesiveness with the sealing member to be bonded.

As such a resin sealing material, it is preferable to use a thermosetting resin.

As the thermosetting adhesive, for example, a resin containing a compound having an ethylenic double bond at the terminal or side chain of the molecule and a thermopolymerization initiator as the main components can be used. More specifically, a thermosetting adhesive made of epoxy resin, acrylic resin or the like can be used. Further, a melt type thermosetting adhesive may be used depending on the laminating apparatus and the curing processing apparatus used in the manufacturing process of the organic EL element.

Further, it is also preferable to use a photocurable resin as such a resin sealing material. For example, a photo-radical-polymerizable resin mainly containing various (meth)acrylates such as polyester (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, polyurethane (meth)acrylate, and epoxy and vinyl ether. Examples include a cationic photopolymerizable resin containing a resin as a main component and a thiol/ene addition type resin. Among these photo-curable resins, epoxy resin-based photo-cationic polymerizable resins, which have low shrinkage of the cured product, little outgas, and excellent long-term reliability, are preferable.

Further, as such a resin sealing material, a chemically curable (two liquid mixture) resin can be used. Further, hot-melt type polyamide, polyester and polyolefin can be used. Further, a cation curing type ultraviolet curing epoxy resin can be used.

The organic material forming the organic EL element may be deteriorated by heat treatment. Therefore, it is preferable to use a resin sealing material that can be adhesively cured from room temperature to 80°C.

[4] Organic polymer layer In the present invention, at least one organic polymer layer on the substrate, a laminate of the first gas barrier layer and the second gas barrier layer, or the non-transition metal (M1 ) And a gas barrier layer containing the complex oxide of the transition metal (M2) are laminated to improve the adhesion between the base material and the sealing layer, and the organic functional layer and the sealing layer. This is a preferred embodiment from the viewpoint of preventing damages and defects of the layer due to mechanical or thermal stress to the sealing layer due to environmental changes and suppressing deterioration of gas barrier properties.

2A and B can be referred to for a preferable layer structure.

Examples of the resin used for the organic polymer layer according to the present invention include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, and alkyl titanate. Can be used alone or in combination of two or more.

Preferably, a polymerizable composition containing the following polymerizable compound, a silane coupling agent, and a polymerization initiator may be layered and then cured to form the composition.

In the present invention, as a method for forming a layer of the polymerizable composition, it can be formed by coating the substrate and the organic EL element with the polymerizable composition. Any appropriate method can be adopted as a method of applying the coating composition. Specific examples thereof include a spin coating method, a roll coating method, a flow coating method, an inkjet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method and a gravure printing method. After applying the coating solution, it is preferable to dry the coating film. The organic solvent contained in the coating film can be removed by drying the coating film. Regarding the forming method, refer to paragraphs “0058” to “0064” of JP-A-2014-151571 and paragraphs “0052” to “0056” of JP-A-2011-183773 that are conventionally known. You can

Among the above-mentioned coating methods, since there is a concern that the electronic device may be deteriorated by moisture or a hydrophilic solvent, general solvent coating is not preferable, and coating is performed in a nitrogen atmosphere without solvent or with a small content of hydrophilic solvent. An inkjet method using the composition can be preferably applied. The inkjet method can be adopted with reference to the technical contents described in, for example, International Publication No. 2014/176365, International Publication No. 2015/100375, International Publication No. 2015/112454 and the like. Specifically, it is also a preferable embodiment to form the organic polymer layer using YIELDjet (registered trademark) Platform manufactured by Kateeva.

Further, as another method for forming a layer of the polymerizable composition, a known vapor deposition method such as a flash vapor deposition method can be used.

For example, a polymerizable composition containing a polymerizable compound, a silane coupling agent and a polymerization initiator may be volatilized by heating under a reduced pressure atmosphere to form a vapor deposition film on a substrate, an electrode layer or an organic functional layer. preferable.

As a method for forming the vapor deposition film, known methods such as those described in JP-A-2008-142941, JP-A-2004-314626 and the like can be used.

As an example, a substrate and an organic functional layer formed thereon are installed in a vacuum apparatus, the polymerizable composition is placed in a heating boat installed in the vacuum apparatus, and the polymerization is performed under a reduced pressure of about 10 Pa. The vapor-deposited film can be formed so as to have a desired layer thickness while heating the functional composition to about 200° C. and covering the base material and the organic functional layer.

The obtained vapor-deposited film is irradiated with ultraviolet rays in a vacuum environment using a high-pressure mercury lamp or the like to cure the vapor-deposited polymerizable composition to form an organic polymer layer.

(Polymerizable compound)
The polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain, or a compound having an epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth)acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride and the like, with (meth)acrylate compounds being preferred. As the (meth)acrylate compound, (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate and the like are preferable. As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

(Silane coupling agent)
The silane coupling agent used in the present invention is, for example, a halogen-containing silane coupling agent (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane). Silane), epoxy group-containing silane coupling agent [2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxy) Cyclohexyl)propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc.], amino group-containing silane cup Ring agent (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-[N-(2-aminoethyl)amino]ethyltrimethoxysilane, 3-[N- (2-Aminoethyl)amino]propyltrimethoxysilane, 3-(2-aminoethyl)amino]propyltriethoxysilane, 3-[N-(2-aminoethyl)amino]propyl-methyldimethoxysilane, etc.), mercapto Group-containing silane coupling agent (2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agent (vinyltrimethoxysilane, vinyltriethoxysilane) Etc.), (meth)acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.) and the like. Among these, a silane coupling agent containing a (meth)acryloyl group (a silane coupling agent containing a (meth)acryloyl group) is preferably used.

Further, as other (meth)acryloyl group-containing silane coupling agents, 1,3-bis(acryloyloxymethyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis(methacryloyloxymethyl) )-1,1,3,3-Tetramethyldisilazane, 1,3-bis(γ-acryloyloxypropyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis(γ-methacryloyl) (Oxypropyl)-1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane , Methacryloyloxymethylmethylpolysilazane, 3-acryloyloxypropylmethyltrisilazane, 3-methacryloyloxypropylmethyltrisilazane, 3-acryloyloxypropylmethyltetrasilazane, 3-methacryloyloxypropylmethyltetrasilazane, 3-acryloyloxypropylmethylpolysilazane , 3-methacryloyloxypropylmethylpolysilazane, acryloyloxymethylpolysilazane, methacryloyloxymethylpolysilazane, 3-acryloyloxypropylpolysilazane, 3-methacryloyloxypropylpolysilazane are preferable, and further, from the viewpoint of easy compound synthesis/identification, 1,3-bis(acryloyloxymethyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis(methacryloyloxymethyl)-1,1,3,3-tetramethyldisilazane, 1, 3-bis(γ-acryloyloxypropyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis(γ-methacryloyloxypropyl)-1,1,3,3-tetramethyldisilazane Particularly preferred.

As the silane coupling agent used in the present invention, the compounds shown below are preferably used. For the synthesis method of the silane coupling agent, reference can be made to JP-A-2009-67778.

（式中、ＲはＣＨ_２＝ＣＨＣＯＯＣＨ_２を表す。）
（重合開始剤）
本発明における重合性組成物は、通常、重合開始剤を含む。重合開始剤を用いる場合、その含有量は、重合に関与する化合物の合計量の０．１モル％以上であることが好ましく、０．５〜２モル％であることがより好ましい。このような組成とすることにより、活性成分生成反応を経由する重合反応を適切に制御することができる。光重合開始剤の例としてはＢＡＳＦジャパン社から市販されているイルガキュア（Ｉｒｇａｃｕｒｅ）シリーズ（例えば、イルガキュア６５１、イルガキュア７５４、イルガキュア１８４、イルガキュア２９５９、イルガキュア９０７、イルガキュア３６９、イルガキュア３７９、イルガキュア８１９など）、ダロキュア（Ｄａｒｏｃｕｒｅ）シリーズ（例えば、ダロキュアＴＰＯ、ダロキュア１１７３など）、クオンタキュア（Ｑｕａｎｔａｃｕｒｅ）ＰＤＯ、ランベルティ（Ｌａｍｂｅｒｔｉ）社から市販されているエザキュア（Ｅｚａｃｕｒｅ）シリーズ（例えば、エザキュアＴＺＭ、エザキュアＴＺＴ、エザキュアＫＴＯ４６など）等が挙げられる。

(In the formula, R represents CH ₂ ═CHCOOCH _2. )
(Polymerization initiator)
The polymerizable composition in the invention usually contains a polymerization initiator. When a polymerization initiator is used, its content is preferably 0.1 mol% or more, and more preferably 0.5 to 2 mol% of the total amount of the compounds involved in the polymerization. With such a composition, the polymerization reaction via the active ingredient forming reaction can be appropriately controlled. Examples of the photopolymerization initiator are commercially available from BASF Japan Ltd. (Irgacure) series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.), Darocure series (eg, Darocure TPO, Darocure 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, commercially available from Lamberti). Etc.) and the like.

In the present invention, a polymerizable composition containing a silane coupling agent, a polymerizable compound, and a polymerization initiator is cured with light (for example, ultraviolet rays), electron beams, or heat rays, but it is preferable to cure with light. .. In particular, it is preferable that the polymerizable composition is heated at a temperature of 25° C. or higher (for example, 30 to 130° C.) and then cured. With such a constitution, the hydrolysis reaction of the silane coupling agent is allowed to proceed, the polymerizable composition is effectively cured, and the film is formed without damaging the base material or the organic functional layer. You can

The light to be applied is usually ultraviolet rays from a high pressure mercury lamp or a low pressure mercury lamp. The radiation energy is preferably 0.1 J / cm ² or more, 0.5 J / cm ² or more is more preferable. When a (meth)acrylate compound is used as the polymerizable compound, the oxygen concentration in the polymerization or the oxygen partial pressure during the polymerization is preferably low because the polymerization is affected by the oxygen in the air. When the oxygen concentration during polymerization is reduced by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, more preferably 0.5% or less. When the oxygen partial pressure at the time of polymerization is reduced by the depressurization method, the total pressure is preferably 1000 Pa or less, more preferably 100 Pa or less. Further, it is particularly preferable to carry out ultraviolet polymerization by irradiating energy of 0.5 J/cm ² or more under a reduced pressure condition of 100 Pa or less.

The organic polymer layer according to the present invention is preferably smooth and has high film hardness. The smoothness of the organic layer is preferably less than 1 nm as average roughness (Ra value) of 1 μm square, and more preferably less than 0.5 nm. The polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 92% or more. The term "polymerization rate" as used herein means the ratio of the reacted polymerizable groups to all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture. The polymerization rate can be quantified by an infrared absorption method.

The layer thickness of the organic polymer layer is not particularly limited, but if it is too thin, it becomes difficult to obtain a uniform layer thickness, and if it is too thick, cracks occur due to external force and the gas barrier property deteriorates. From this viewpoint, the thickness of the organic layer is preferably 50 to 2000 nm, more preferably 200 to 1500 nm.

The surface of the organic polymer layer is required to be free of foreign matter such as particles and protrusions. Therefore, it is preferable that the organic polymer layer is formed in a clean room. The cleanliness is preferably class 10000 or less, more preferably class 1000 or less. Higher hardness of the organic layer is preferable. When the hardness of the organic layer is high, the inorganic layer is formed smoothly, and as a result, the barrier ability is improved. The hardness of the organic layer can be expressed as a micro hardness based on the nanoindentation method. The microhardness of the organic layer is preferably 100 N/mm or more, and more preferably 150 N/mm or more.

(Lamination of organic polymer layer and sealing layer)
The organic polymer layer and the sealing layer can be laminated by sequentially and repeatedly forming the organic polymer layer and the sealing layer according to a desired layer configuration. Particularly, in the present invention, when at least two organic polymer layers and at least two sealing layers are alternately laminated, a high gas barrier property can be exhibited, which is preferable (see FIGS. 2A and 2B).

[5] Other functional layers [Protective layer]
A protective layer made of a polysiloxane modified layer or the like may be formed on the outermost layer of the sealing layer according to the present invention on the side where the sealing layer is formed on the substrate. The polysiloxane modified layer is formed by applying a coating solution containing polysiloxane by a wet coating method and drying it, and then subjecting the dried coating film to modification treatment by heating, irradiation with ultraviolet light, irradiation with vacuum ultraviolet light, etc. It can be formed by performing the modification treatment of. As the vacuum ultraviolet light, it is preferable to use VUV used for the modification treatment of the polysilazane described above.

In addition, regarding the details of polysiloxane, the paragraphs “0028” to “0032” of JP 2013-151123 A, the paragraphs “0050” to “0064” of JP 2013-086501, which are publicly known, and JP 2013 are known. It can be adopted by referring to paragraphs “0063” to “0081” of JP-059927A, paragraphs “0119” to “0139” of JP2013-226673A, and the like.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, “parts” or “%” is used, but unless otherwise specified, “parts by mass” or “% by mass” is shown.

Example 1
<Production of evaluation device>
According to the so-called Electrical Calcium Test method (for example, see US Pat. No. 8,664,963) known as a method for measuring a water vapor transmission rate (WVTR) utilizing a change in electric resistance value of a Ca thin film. An evaluation device imitating an electronic device was produced.

The configuration of the evaluation device is shown in FIG.

<Preparation of substrate>
As the base material, a glass plate having a thickness of 0.7 mm and a size of 50 mm×50 mm was used.

<Formation of Ca vapor deposition layer and aluminum electrode>
For the Ca vapor deposition layer, one side of the 50 mm×50 mm size non-alkali glass plate (thickness 0.7 mm) was UV-cleaned. Ca was vapor-deposited with a size of 14 mm×20 mm through a mask in the center of the glass plate using a vacuum vapor deposition device manufactured by ALS Technology Co., Ltd. The thickness of the Ca vapor deposition layer was 80 nm. Next, the mask was exchanged, and aluminum was vapor-deposited so as to have a thickness of 200 nm in the pattern shown in FIG. 4 to form electrodes. The area of the Ca vapor deposition layer not covered by the aluminum electrode was 10 mm×20 mm.

<Formation of organic polymer layer of evaluation device>
The organic polymer layer was formed by a known flash vapor deposition method. The following mixture was used as a raw material for the organic polymer layer.

1,9-Nonanediol diacrylate 75 parts by weight Trimethylolpropane triacrylate 14 parts by weight Phenoxyethyl acrylate 6 parts by weight 2,4,6-Trimethylbenzophenone 5 parts by weight Was ² J/cm ² .

A mask was used to form the organic polymer layer, and the organic polymer layer was formed in the center of the glass plate to have a size of 26 mm×26 mm. The thickness of the organic polymer layer was set to 1 μm in the size of 22 mm×22 mm in the central portion covering the Ca vapor deposition range, and the layer thickness was gradually reduced outside the central portion 22 mm×22 mm.

<Formation of evaluation device sealing layer (gas barrier layer)>
(Sputtering film forming method and film forming condition)
For forming the sealing layer (gas barrier layer), a magnetron sputtering apparatus (manufactured by Canon Anelva: Model EB1100) was used as a vapor phase method/sputtering apparatus.

Each of the following targets was used as a target, Ar and O ₂ were used as a process gas, and film formation was performed by an RF method or a DC method using a magnetron sputtering apparatus. Sputtering power was set to 5.0 W/cm ² unless otherwise specified, and the film forming pressure was 0.4 Pa. The oxygen partial pressure was adjusted under each film forming condition. It should be noted that, by filming using a glass substrate in advance, data on the change in layer thickness with respect to the film forming time was taken under each film forming condition, and the layer thickness formed per unit time was calculated, and then the set layer thickness was calculated. The film formation time was set so that

In the lamination of the organic polymer layer and the gas barrier layer, the movement of the base material between the film forming devices was carried out while maintaining the reduced pressure state.

<target>
T1: A commercially available polycrystalline silicon target was used.

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

T3: A commercially available metal Nb target was used.

T4: A commercially available metal Ta target was used.

T5: Si and Nb powders pulverized so that Si was 80 atomic% and Nb was 20 atomic% were mixed, and hot pressed in an Ar atmosphere to perform sintering. After the sintered mixed material was machine-molded, it was bonded on a copper back plate to obtain a target.

T6: Nb ₂ O ₅ powder in an amount of 50% by mass and SiO ₂ powder in an amount of 50% by mass were mixed in a ball mill with distilled water as a dispersant, and the resulting slurry was granulated using a spray drier to obtain a _secondary powder. An oxide mixed powder having a particle size of 20 to 100 μm was obtained.

On the other hand, a copper backing plate with a diameter of 6 inches (1 inch is 2.54 cm) was used as the target holder. Then, the surface portion of the backing plate on which the oxide mixed powder was to be sprayed was roughened by sandblasting using Al ₂ O ₃ abrasive grains to make it a rough surface.

Next, an Ni-Al (mass ratio 8:2) alloy powder is plasma sprayed (using a Metco sprayer) in a reducing atmosphere to form an undercoat of Ni-Al (mass ratio 8:2) having a layer thickness of 50 μm. Then, the above oxide mixed powder was plasma sprayed on the undercoat under a reducing atmosphere to prepare a target. The obtained target is an oxygen-deficient target containing Si at a ratio of 40 atom% and Nb at a ratio of 60 atom %.

<Film forming conditions>
T1-1: T1 was used as a target, and sputtering deposition was performed by the RF method. The sputtering power source power was 4.0 W/cm ² and the oxygen partial pressure was 20%. Further, the film formation time was set so that the layer thickness was 100 nm.

T1-2: Performed in the same manner as T1-1, except that the film formation time was set so that the layer thickness was 90 nm.

T1-3: Performed in the same manner as T1-1, except that the film formation time was set so that the layer thickness was 200 nm.

T1-4: The same procedure as T1-1 was performed except that the film formation time was set so that the layer thickness was 40 nm.

T2-1: Using T2 as a target, a film was formed by a DC method. The oxygen partial pressure was 12%. Further, the film formation time was set so that the layer thickness was 10 nm.

T2-2: The same procedure as T2-1 was performed except that the film formation time was set so that the layer thickness was 5 nm.

T3-1: Using T1 and T3, two-way simultaneous sputtering was performed by the DC method. The oxygen partial pressure was 18%. As the composition of the barrier layer, the power supply power at T1 and the power supply power at T3 were adjusted so that the atomic ratios of Si and Nb were the same. Further, the film formation time was set so that the layer thickness was 50 nm.

T4-1: Using T1 and T4, two-source simultaneous sputtering was performed by the DC method. The oxygen partial pressure was 18%. As the composition of the barrier layer, the power supply power at T1 and the power supply power at T4 were adjusted so that the atomic ratios of Si and Ta were the same. Further, the film formation time was set so that the layer thickness was 50 nm.

T5-1: T5 was used as a target to form a film by the DC method. The oxygen partial pressure was 18%. Further, the film formation time was set so that the layer thickness was 50 nm.

T6-1: T6 was used as a target to form a film by the DC method. The oxygen partial pressure was 10%. Further, the film formation time was set so that the layer thickness was 50 nm.

T6-2: The same process as T6-1 was performed except that the film forming time was set so that the layer thickness was 30 nm.

<Measurement of composition distribution in the thickness direction of the sealing layer>
The composition distribution profile in the thickness direction of the sealing layer was measured by XPS analysis. The XPS analysis conditions are as follows.

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

(Measurement of thickness of composite composition area)
Taking the case where the transition metal is Nb as an example, the composition of the sealing layer can be represented by (Si)(Nb) _x O _y N _z from the data obtained from the XPS composition analysis. In the aspect in which the first layer and the second layer are laminated, Si which is a non-transition metal and Nb which is a transition metal coexist in the interface region between the first layer and the second layer, and the transition metal Nb/Si A region in which the value x of the atomic number ratio of is within the range of 0.02≦x≦49 is defined as “composite composition region”, and the presence or absence of the region and the thickness (nm) thereof were measured and described in the table. The same measurement is performed in the case where the sealing layer is formed as a composite oxide layer of Si that is a non-transition metal and Nb (or Ta) that is a transition metal, and the thickness (nm) of the region is described in the table. did.

(Calculation of oxygen deficiency index in the composite composition region)
The value of (2y+3z)/(a+bx) at each measurement point was calculated using the XPS analysis data. Here, since the non-transition metal is Si, a=4, and since the transition metal is Nb or Ta, a=5. The minimum value of (2y+3z)/(a+bx) was determined, and this was shown in Table 1 as an index of oxygen deficiency. When (2y+3z)/(a+bx)<1.0, it means that there is an oxygen deficiency state.

<Production of evaluation device 101>
A Ca vapor deposition layer and an aluminum electrode were formed on a glass plate, and then, as shown in Table 1, a sealing layer was formed under the film forming condition: T1-1 to obtain an evaluation device 101.

<Production of Evaluation Devices 102 to 115>
Similarly, the sealing layers were formed with the combinations shown in Table 1 to obtain evaluation devices 102 to 115.

<<Evaluation>>
After measuring the initial resistance value between the electrodes of each evaluation device, each evaluation device was stored in the environment of 60° C. and 90% RH with the wiring connected to the measuring device, and the change with time of the resistance value was measured. .. The time when the resistance value increased 1.1 times from the initial resistance value was calculated, and the rank of the gas barrier property was calculated according to the following evaluation index, and the results are shown in the table.

表１から、本発明に係る評価デバイスは比較例に対してガスバリアー性に優れており、本発明の封止層（ガスバリアー層）及び封止方法は、薄層でも極めて高いガスバリアー性能を有する効率的な封止層及び封止方法であることが分かった。<Gas barrier property rank>
1: Less than 20 hr 2: 20 hr or more, less than 50 hr 3: 50 hr or more, less than 100 hr 4: 100 hr or more, less than 200 hr 5: 200 hr or more

From Table 1, the evaluation device according to the present invention is superior in gas barrier property to the comparative example, and the sealing layer (gas barrier layer) and the sealing method of the present invention show extremely high gas barrier performance even in a thin layer. It has been found to be an efficient sealing layer and sealing method to have.

Example 2
<Production of electronic device 201>
<Production of base material>
As the resin base material, a 100-μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48) manufactured by Toray Industries, Inc.) having both sides subjected to easy adhesion treatment was used. A clear hard coat layer having a thickness of 0.5 μm and having an antiblock function was formed on the surface of the resin substrate opposite to the surface on which the gas barrier layer was formed. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied on a resin base material so that the dry layer thickness was 0.5 μm, followed by drying at 80° C., and then under air, high pressure. Curing was performed using a mercury lamp under the condition of an irradiation energy amount of 0.5 J/cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed on the surface of the resin base material on which the gas barrier layer was formed as follows. UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Co., Ltd. is applied to a resin base material so that the dry layer thickness is 2 μm, followed by drying at 80° C., and then using a high pressure mercury lamp under air. And the irradiation energy amount was 0.5 J/cm ² . Thus, a resin substrate with a clear hard coat layer was obtained. Hereinafter, in this example and the comparative example, the resin substrate with the clear hard coat layer is simply used as the substrate for convenience.

<Formation of gas barrier layer (coating modification method)>
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (NN120-20, manufactured by AZ Electronic Materials) and an amine catalyst (N,N,N',N'-tetramethyl-1,6-diaminohexane (TMDAH). )) perhydropolysilazane 20% by weight dibutyl ether solution (AZ Electronic Materials Co., Ltd., NAX120-20) is mixed at a ratio of 4:1 (mass ratio), and further for adjusting the dry layer thickness. A coating solution was prepared by appropriately diluting with dibutyl ether.

The surface of the base material on which the functional layer is to be formed was coated with the above coating solution by a spin coating method so that the dry layer thickness was 250 nm, and dried at 80° C. for 2 minutes. Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment under the condition of an irradiation energy of 6 J/cm ² using a vacuum ultraviolet ray irradiation device having a Xe excimer lamp having a wavelength of 172 nm. At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was 0.1% by volume. Further, the stage temperature at which the sample is set is set to 80°C. This operation was repeated once again to form two gas barrier layers by the coating modification method.

A substrate having a gas barrier property produced in this manner is cut into a size of 50 mm×50 mm, and a bottom emission type organic electroluminescence device (organic EL device) is cut by using the substrate as a substrate as described below. It was made.

<Organic functional layer: Fabrication of organic EL device>
On the gas barrier layer of the base material, an anode, a lead wire, an organic functional layer, and a cathode were sequentially formed. Each layer was formed in a shape such that a light emitting region of 30 mm×30 mm was obtained in the center of the base material. An ITO layer having a thickness of 150 nm was formed as an anode by a high frequency sputtering method, and an aluminum layer having a thickness of 300 nm was formed as a takeout wiring. As the organic functional layer, a hole injection layer (copper phthalocyanine (CuPc), thickness 30 nm)/hole transport layer (NPD, thickness 100 nm)/fluorescent blue light emitting layer (thickness 30 nm)/electron transport layer ( Aluminum quinolate (Alq ₃ ) and a thickness of 30 nm/electron injection layer (lithium fluoride, thickness of 1 nm) were formed in this order, and a 200 nm-thick aluminum layer was formed as a cathode.

<Formation of sealing layer>
(Formation of organic polymer layer)
An organic polymer layer was formed in the same manner as in Example 1. A mask was used to form the organic polymer layer, and the organic polymer layer was formed in the center of the substrate so as to have a size of 38 mm×38 mm. The thickness of the organic polymer layer was 2 μm in the size of the central portion 34 mm×34 mm covering the light emitting region, and the layer thickness was gradually reduced outside the central portion 34 mm×34 mm.

(Formation of gas barrier layer)
A gas barrier layer having a thickness of 200 nm was formed on the organic polymer layer under the film forming condition of T1-3. When forming the gas barrier layer, the film formation range was set to be larger than the organic polymer layer formation range, and the film formation was performed by masking so as not to cover the electrode contact portion.

Further, in the same manner, another layer of the organic polymer layer and another layer of the gas barrier layer were formed to form a sealing layer.

(Lamination of protective film)
An adhesive layer was formed on the surface of the resin substrate on which the clear hard coat was formed, which was used as the substrate of the device, on which the clear hard coat layer having a thickness of 2 μm was formed, to obtain a protective film. The size of the protective film was set so as not to cover the electrode contact portion when it was attached to the device. Take out the device with the encapsulation layer inside the glove box, place the protective film that has been dried in the glove box in advance so that the adhesive layer surface and the device encapsulation layer surface are in contact, and bond by vacuum lamination. did. In this way, the electronic device 201 of the comparative example was obtained.

The sealing layer of the electronic device 201 does not have a composite composition region.

<Production of electronic device 202>
An electronic device 202 of a comparative example was obtained in the same manner as the electronic device 201, except that the gas barrier layer was formed as follows.

The sealing layer of the electronic device 202 does not have a composite composition region.

(Formation of gas barrier layer)
A commercially available batch type plasma CVD apparatus was used. The substrate was set in a vacuum apparatus and evacuated to the order of 10 ⁻⁴ Pa, and then silane and nitrogen were used as source gases, and a 50 nm silicon nitride layer was formed by plasma CVD.

<Production of electronic device 203>
The present invention was performed in the same manner as in the electronic device 201 except that the gas barrier layer was formed in the same film formation conditions as T1-4 and T2-1 in the same manner as in the evaluation device 105, except that the gas barrier layer having a thickness of 50 nm was formed. The electronic device 203 of was obtained.

The sealing layer of the electronic device 203 had two 22 nm composite composition regions in the thickness direction. In addition, the minimum value of (2y+3z)/(a+bx) in the two composite composition regions was 0.65, which was an oxygen-deficient composition.

<<Evaluation>>
Each electronic device was wound around a metal roller having a diameter of 75 mm and left in a constant temperature and humidity chamber under high temperature and high humidity (temperature 60° C., relative humidity 90%). Each of the electronic devices was taken out from the constant temperature and humidity chamber at regular intervals, and light was emitted at room temperature to confirm the presence or absence of dark spots. This work is continued until the dark spot area ratio in the light emitting region reaches 1%, and the time from when the dark spot area ratio reaches 1% after being left in the constant temperature and humidity chamber is evaluated as the gas barrier property. did. The longer the time, the higher the gas barrier property.

As a result, the time required for the dark spot area ratio to reach 1% was 50 hours for the electronic device 201 of the comparative example and 200 hours for the electronic device 202 of the comparative example, while the electronic device of the present invention. 203 was 1500 hours, which was very good.

As a result of the evaluation, in the electronic device of the present invention, the generation of dark spots is suppressed as compared with the comparative example, and the sealing layer and the sealing method of the present invention show an extremely high gas barrier performance even in a thin layer, and are efficient. It was found that it was a different sealing layer and sealing method.

Example 3
An evaluation device having a Ca thin film was prepared in the same manner as in Example 1. Further, an organic polymer layer was similarly formed.

<Formation of sealing layer (gas barrier layer) of evaluation device>
(Gas barrier layer 1: formation of non-transition metal (M1)-containing layer)
Polysilazane containing Si was used as the non-transition metal (M1), and a non-transition metal (M1)-containing layer was formed by a coating/modifying method. The forming conditions are shown in Table 2 by combining the following coating conditions P-1 to P-4 and modification conditions V-1 to V-5.

P-1: A dibutyl ether solution containing 20% by mass of perhydropolysilazane (NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst (N,N,N,N'-tetramethyl-1,6-diamino). Hexane (TMDAH))-containing perhydropolysilazane 20 mass% dibutyl ether solution (AZ Electronic Materials Co., Ltd., NAX120-20) was mixed at a ratio of 4:1 (mass ratio), and further dried layer thickness. For adjustment, it was appropriately diluted with dehydrated dibutyl ether to prepare a coating solution.

The central portion of the evaluation device was masked at other portions so as to be applied in a range of 36 mm×36 mm, and the above coating solution was dried by spin coating under a nitrogen atmosphere in a glove box to a dry layer thickness of 100 nm. And was dried at 80° C. for 10 minutes.

P-2: Same as P-1, except that the dry layer thickness was 250 nm.

P-3: Same as P-1, except that the dry layer thickness was 40 nm.

P-4: A dibutyl ether solution containing 20% by mass of perhydropolysilazane (NN120-20, manufactured by AZ Electronic Materials Co., Ltd.) and ALCH (aluminum ethyl acetoacetate/diisopropylate) were used as Al atoms to Si atoms 100 Were mixed in such a ratio that the number of the above was 1, and appropriately diluted with dehydrated dibutyl ether to adjust the dry layer thickness, to prepare a coating solution. Then, it was applied by the same method as P-1 so that the dry layer thickness was 80 nm, and dried at 80° C. for 10 minutes.

V-1: The sample on which the non-transition metal (M1)-containing layer was formed was installed in the vacuum ultraviolet irradiation device shown in FIG. 5 having a Xe excimer lamp with a wavelength of 172 nm, and vacuumed under the condition of irradiation energy of 5.0 J/cm ^2. Ultraviolet irradiation treatment was performed. At this time, nitrogen and oxygen were supplied into the chamber to adjust the oxygen concentration of the irradiation atmosphere to 0.1% by volume. Further, the stage temperature at which the sample is set is set to 80°C.

In the vacuum ultraviolet light irradiating device (100) shown in FIG. 5, 101 is a device chamber, in which an appropriate amount of nitrogen and oxygen is supplied to the inside from a gas supply port (not shown) and exhausted from a gas discharge port (not shown) to form a chamber. By substantially removing water vapor from the inside, the oxygen concentration in the chamber can be maintained at a predetermined concentration. Reference numeral 102 denotes an Xe excimer lamp (excimer lamp light intensity: 130 mW/cm ² ) having a double tube structure for irradiating vacuum ultraviolet light of 172 nm, and 103 denotes an excimer lamp holder which also serves as an external electrode. 104 is a sample stage. The sample stage 104 can be horizontally reciprocated at a predetermined speed in the apparatus chamber 101 by a moving unit (not shown). Further, the sample stage 104 can be maintained at a predetermined temperature by a heating unit (not shown). Reference numeral 105 is 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 coating layer of the sample and the excimer lamp tube surface is 3 mm. Reference numeral 106 denotes a light-shielding plate that prevents the coating layer of the sample from being irradiated with vacuum ultraviolet light during aging of the Xe excimer lamp 102.

The energy applied to the surface of the sample coating layer in the vacuum ultraviolet light irradiation step was measured using an ultraviolet integrating photometer C8026/H8025 UV POWER METER manufactured by Hamamatsu Photonics KK using a 172 nm sensor head. At the time of measurement, the sensor head is installed in the center of the sample stage 104 such 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 in the irradiation step, and the sample stage 104 was moved at a speed of 0.5 m/min for measurement. 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 in this measurement, the moving speed of the sample stage was adjusted so that the irradiation energy amount was 5.0 J/cm ² . The vacuum ultraviolet light irradiation was performed after aging for 10 minutes.

V-2: Same as V-1 except that the irradiation energy was 3.5 J/cm ² .

V-3: Same as V-1 except that the irradiation energy was 1.0 J/cm ² .

V-4: Same as V-1 except that the irradiation energy was 0.5 J/cm ² .

V-5: No vacuum ultraviolet light irradiation treatment was performed.

(Gas barrier layer 2: formation of transition metal (M2) containing layer or (M2) non-containing layer)
It was formed by a vapor phase method and sputtering. As the sputtering device, a magnetron sputtering device (manufactured by Canon Anerva Co.: model EB1100) was used.

As targets, the following targets T1 to T4 used in Example 1 were used, Ar and O ₂ were used as process gas, and film formation was performed by an RF method or a DC method using a magnetron sputtering apparatus. It was Sputtering power was set to 5.0 W/cm ² unless otherwise specified, and the film forming pressure was 0.4 Pa. The oxygen partial pressure was adjusted under each film forming condition. It should be noted that, by filming using a glass substrate in advance, data on the change in layer thickness with respect to the film forming time was taken under each film forming condition, and the layer thickness formed per unit time was calculated, and then the set layer thickness was calculated. The film formation time was set so that

The following film forming conditions were applied to each sample and shown in Table 2.

<target>
T1: A commercially available polycrystalline silicon target was used.

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

T3: A commercially available metal Nb target was used.

T4: A commercially available metal Ta target was used.

<Film forming conditions>
T1-1: Using T1 as a target, a film was formed by an RF method. The sputtering power source power was 4.0 W/cm ² and the oxygen partial pressure was 20%. Further, the film formation time was set so that the layer thickness was 100 nm.

T1-2: Performed in the same manner as T1-1 except that the film formation time was set so that the layer thickness was 10 nm.

T2-1: Using T2 as a target, a film was formed by a DC method. The oxygen partial pressure was 12%. Further, the film formation time was set so that the layer thickness was 10 nm.

T2-2: The same procedure as T2-1 was performed except that the film formation time was set so that the layer thickness was 5 nm.

T2-3: The same procedure as T2-1 was performed except that the film formation time was set so that the layer thickness was 2 nm.

T3-1: Using T3 as a target, a film was formed by a DC method. The oxygen partial pressure was 20%. Further, the film formation time was set so that the layer thickness was 10 nm.

T4-1: Using T4 as a target, a film was formed by the DC method. The oxygen partial pressure was 20%. Further, the film formation time was set so that the layer thickness was 10 nm.

<Production of Evaluation Devices 301 to 317>
In the same manner as in Example 1, a Ca vapor deposition layer and an aluminum electrode were formed on a glass plate, and then a sealing layer was formed under each condition as shown in Table 2 to give evaluation devices 301 to 317. Obtained.

<Measurement of composition distribution in the thickness direction of the sealing layer>
The composition distribution profile in the thickness direction of the sealing layer was measured by the XPS analysis used in Example 1. The analyzed elements are Si, Nb, Ta, Al, O, N and C.

In the sample using P-4 manufactured this time, Al was not detected in the region containing the composite oxide of (M1) and (M2).

(Measurement of thickness of composite composition area)
The presence or absence of the composite composition region and its thickness (nm) were measured in the same manner as in Example 1 and are listed in the table.

(Calculation of oxygen deficiency index in the composite composition region)
Using the above XPS analysis data, the value of (2y+3z)/(a+bx) at each measurement point was calculated in the same manner as in Example 1. Listed in the table. When (2y+3z)/(a+bx)<1.0, it means that there is an oxygen deficiency state.

<<Evaluation>>
After measuring the initial resistance value between the electrodes of each evaluation device, each evaluation device was stored in an environment of 85° C. and 85% RH with the wiring connected to the measuring device, and the change with time of the resistance value was measured. .. The time when the resistance value doubled from the initial resistance value was calculated, and the rank of gas barrier property was calculated according to the following evaluation index, and the results are shown in Table 2.

表２から、評価の結果、本発明に係る評価デバイスは比較例に対してガスバリアー性に優れており、本発明の封止層及び封止方法は、薄層でも極めて高いガスバリアー性能を有する効率的な封止層及び封止方法であることが分かった。(Gas barrier property rank)
1: Less than 50 hr 2: 50 hr or more, less than 100 hr 3: 100 hr or more, less than 200 hr 4: 200 hr or more, less than 300 hr 5: 300 hr or more, less than 400 hr 6: 400 hr or more, less than 500 hr 7: 500 hr or more

From Table 2, as a result of the evaluation, the evaluation device according to the present invention is superior to the comparative example in gas barrier properties, and the sealing layer and the sealing method of the present invention have extremely high gas barrier performance even in a thin layer. It has been found to be an efficient sealing layer and sealing method.

Example 4
<Production of electronic device 401>
[Production of base material]
As the resin base material, a polyethylene terephthalate film roll (Lumirror (registered trademark) (U48) manufactured by Toray Industries, Inc.) having a thickness of 100 μm and having both sides subjected to easy adhesion treatment was used. A clear hard coat layer having a thickness of 0.5 μm and having an antiblock function was formed by a roll-to-roll method on the surface of the resin substrate opposite to the surface on which the gas barrier layer was formed. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied on a resin base material so that the dry layer thickness was 0.5 μm, followed by drying at 80° C., and then under air, high pressure. Curing was performed using a mercury lamp under the condition of an irradiation energy amount of 0.5 J/cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed on the surface of the resin base material on which the gas barrier layer was formed as follows. UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Co., Ltd. is applied to a resin base material so that the dry layer thickness is 2 μm, followed by drying at 80° C., and then using a high pressure mercury lamp under air. And the irradiation energy amount was 0.5 J/cm ² . In this way, a resin base material roll with a clear hard coat layer was obtained. Hereinafter, in this example and the comparative example, the resin substrate with the clear hard coat layer is simply used as the substrate for convenience.

<Formation of first gas barrier layer (CVD method)>
The first gas barrier layer is formed on the surface of the substrate roll on which the clear hard coat layer having a thickness of 2 μm is formed by using the CVD film forming apparatus described in the example of JP-A-2015-131473 and using the condition of a4. Formed.

<Formation of second gas barrier layer (coating modification method)>
For forming the second gas barrier layer, a sheet was cut out from the base material roll on which the first gas barrier layer was formed and used.

By laminating on the first gas barrier layer, a second gas barrier layer was formed as follows.

A dibutyl ether solution containing 20% by mass of perhydropolysilazane (NN120-20, manufactured by AZ Electronic Materials) and an amine catalyst (N,N,N',N'-tetramethyl-1,6-diaminohexane (TMDAH). )) perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) is mixed at a ratio of 4:1 (mass ratio) to further adjust the dry layer thickness. A coating solution was prepared by appropriately diluting with dibutyl ether.

The surface of the base material on which the functional layer is to be formed was coated with the above coating solution by a spin coating method so that the dry layer thickness was 250 nm, and dried at 80° C. for 2 minutes. Then, the dried coating film was subjected to vacuum ultraviolet light irradiation treatment under the condition of irradiation energy of 6 J/cm ² using a vacuum ultraviolet light irradiation device having a Xe excimer lamp having a wavelength of 172 nm. At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was 0.1% by volume. In addition, the temperature of the stage on which the sample is placed was set to 80°C. This operation was repeated once again to form two gas barrier layers by the coating modification method.

The substrate having a gas barrier property produced in this manner is cut into a size of 50 mm×50 mm, and using this as a substrate, a bottom emission type organic electroluminescence element (organic EL element) is obtained by the method described below. It was made.

[Functional element: Preparation of organic EL element]
On the gas barrier layer of the base material, an anode, a lead wire, an organic functional layer, and a cathode were sequentially formed. Each layer was formed in a shape such that a light emitting region of 30 mm×30 mm was obtained in the center of the base material. An ITO layer having a thickness of 150 nm was formed as an anode by a high frequency sputtering method, and an aluminum layer having a thickness of 300 nm was formed as a takeout wiring. As the organic functional layer, a hole injection layer (copper phthalocyanine (CuPc), thickness 30 nm)/hole transport layer (NPD, thickness 100 nm)/fluorescent blue light emitting layer (thickness 30 nm)/electron transport layer ( Aluminum quinolate (Alq ₃ ) and a thickness of 30 nm/electron injection layer (lithium fluoride, thickness of 1 nm) were formed in this order, and a 200 nm-thick aluminum layer was formed as a cathode.

[Formation of sealing layer]
<Formation of organic polymer layer>
In the same manner as in Example 2, an organic polymer layer was formed on the functional element. A mask was used to form the organic polymer layer, and the organic polymer layer was formed in the center of the substrate so as to have a size of 38 mm×38 mm. The thickness of the organic polymer layer was 2 μm in the size of the central portion 34 mm×34 mm covering the light emitting region, and the layer thickness was gradually reduced outside the central portion 34 mm×34 mm.

<Formation of non-transition metal (M1)-containing layer>
A layer having a thickness of 100 nm was formed on the organic polymer layer by using the coating condition: P-1 and the modifying condition: V-2. When forming the layer, the film formation range was made larger than the organic polymer layer formation range, and the layer was formed by masking so as not to cover the electrode contact portion.

<Formation of transition metal (M2)-free layer>
A layer having a thickness of 100 nm was formed on the non-transition metal (M1)-containing layer under the film forming condition: T1-1. At the time of layer formation, film formation was performed using a mask so that the film formation range was the same size as the non-transition metal (M1)-containing layer.

Further, similarly, another organic polymer layer, a non-transition metal (M1)-containing layer, and a transition metal (M2)-non-containing layer were formed one by one to obtain a sealing layer.

<Laminating protective film>
An adhesive layer was formed on the surface of the resin substrate on which the clear hard coat was formed, which was used as the substrate of the device, on which the clear hard coat layer having a thickness of 2 μm was formed, to obtain a protective film. The size of the protective film was set so as not to cover the electrode contact portion when it was attached to the device. Remove the device with the encapsulation layer inside the glove box, place the protective film that had been dried in the glove box in advance so that the adhesive layer surface and the device encapsulation layer surface are in contact, and bond by vacuum lamination. did. In this way, the electronic device 401 of the comparative example was obtained.

The sealing layer of the electronic device 401 does not have a composite composition region.

<Production of electronic device 402>
Further, in the same manner as in the electronic device 401 except that an organic polymer layer, a non-transition metal (M1)-containing layer, and a transition metal (M2)-free layer were formed one layer at a time, Comparative Example The electronic device 402 was obtained.

The sealing layer of the electronic device 402 does not have a composite composition region.

<Production of electronic device 403>
An organic polymer layer is formed, and a non-transition metal (M1)-containing layer having a thickness of 40 nm is formed on the organic polymer layer by using coating conditions: P-3 and modification conditions: V-2, and further a film is formed thereon. Condition: A transition metal (M2)-free layer having a thickness of 5 nm was formed using T2-2. An electronic device 403 of the present invention was obtained in the same manner as the electronic device 401, except that this was repeated twice to form the sealing layer.

The sealing layer of the electronic device 403 had two composite composition regions of 18 nm in the thickness direction. In addition, the minimum value of (2y+3z)/(a+bx) in each of the two composite composition regions was 0.66, indicating an oxygen-deficient composition.

<<Evaluation>>
Each electronic device was wound around a metal roller having a diameter of 75 mm and left in a constant temperature and humidity chamber under high temperature and high humidity (temperature 85° C., relative humidity 85%). Each of the electronic devices was taken out from the constant temperature and humidity chamber at regular intervals, and light was emitted at room temperature to confirm the presence or absence of dark spots. This work is continued until the dark spot area ratio in the light emitting region reaches 1%, and the time from when the dark spot area ratio reaches 1% after being left in the constant temperature and humidity chamber is evaluated as the gas barrier property. did. The longer the time, the higher the gas barrier property.

As a result, the time until the dark spot area ratio reached 1% was 100 hours in the electronic device 201 of the comparative example.

Similarly, the electronic device 402 of the comparative example lasted 120 hours. Although the number of laminated sealing layers was increased with respect to the electronic device 401, the performance was hardly improved. This is considered to be due to insufficient durability of the sealing layer at a temperature of 85° C. and a relative humidity of 85%.

On the other hand, the electronic device 403 of the present invention lasted 1000 hours and was very good.

As a result of the evaluation, the electronic device of the present invention has suppressed the generation of dark spots as compared to the comparative example, the sealing layer and the sealing method of the present invention exhibit extremely high gas barrier performance even in a thin layer, and It was found to be an efficient sealing layer and sealing method having high durability under high temperature and high humidity.

The electronic device of the present invention is an electronic device including a sealing layer having high gas barrier performance, and the sealing layer is particularly preferably used for organic EL element applications.

1 substrate 2 electrode (anode, cathode)
3 Organic Functional Layer 4 Sealing Layer 5 First Gas Barrier Layer 6 Second Gas Barrier Layer 7A Composite Composition Area 7B Composite Composition Gas Barrier Layer 8 Gas Barrier Layer 9 Organic Polymer Layer 10 Electronic Device 100 Vacuum Ultraviolet Light Irradiator 101 Apparatus chamber 102 Xe excimer lamp 103 Excimer lamp holder 104 Sample stage 105 Polysilazane compound coating layer forming sample 106 Light-shielding plate

Claims (10)

An electronic device comprising a pair of electrodes on a base material, an organic functional layer including at least one light emitting layer between the electrodes, and a sealing layer arranged on the organic functional layer, wherein the sealing layer is A first gas barrier layer containing an oxide of a non-transition metal (M1) of Groups 12 to 14, and an oxide of a transition metal (M2) disposed in contact with the first gas barrier layer. laminate der of the second gas barrier layer which is, and a part of the thickness direction of the laminate region containing the composite oxide of the non-transition metals (M1) and the transition metal (M2) or there is a laminate existing, or the or a gas barrier layer containing a composite oxide of non-transition metals (M1) and the transition metal (M2), or have a region containing the composite oxide An electronic device as described above. The gas barrier layer or region containing the complex oxide is (M1)(M2) _x O _y N _z, where M1 is a non-transition metal, M2 is a transition metal, O is O and nitrogen is N. The electronic device according to claim 1, further comprising a complex oxide represented by the formula (1) below.
Relational expression (1) (2y+3z)/(a+bx)<1.0
(However, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen, x, y, z: stoichiometric coefficient, 0.02≦x≦49, 0<y, 0≦z, a : Represents the maximum valence of M1, b: represents the maximum valence of M2.) The electronic device according to claim 1 or 2 , wherein the layer containing the non-transition metal (M1) contains polysilazane and a modified product of polysilazane. The electronic device according to any one of claims 1 to 3, wherein the transition metal (M2) is selected from niobium (Nb), tantalum (Ta), and vanadium (V). .. The electronic device according to any one of claims 1 to 4, wherein at least one organic polymer layer is laminated on the functional element. The electronic device according to any one of claims 1 to 5 , wherein the functional element has a pair of electrodes and an organic functional layer including at least one light emitting layer between the electrodes. .. A method for sealing an electronic device, comprising forming a functional element and a sealing layer for sealing the functional element on a base material, wherein at least one non-transition metal of Group 12 to 14 is used as the sealing layer. A laminate of a first gas barrier layer containing an oxide of (M1) and a second gas barrier layer containing an oxide of a transition metal (M2) arranged in contact with the first gas barrier layer. And a laminate in which a region containing a complex oxide of the non-transition metal (M1) and the transition metal (M2) is present in a part of the thickness of the laminate , or the non-transition A gas barrier layer containing a composite oxide of a metal (M1) and the transition metal (M2) or a region containing the composite oxide is formed by a vapor phase film forming method or a coating method. Electronic device sealing method. The first gas barrier layer containing an oxide of the non-transition metal (M1) is formed on the functional element side as the sealing layer, and the electronic device encapsulation according to claim 7. How to stop. A second gas barrier layer containing the oxide of the transition metal (M2) is formed on the first gas barrier layer containing the oxide of the non-transition metal (M1) by a vapor phase film forming method. It forms, The sealing method of the electronic device of Claim 7 or Claim 8 characterized by the above-mentioned. The first gas barrier layer containing an oxide of the non-transition metal (M1) contains polysilazane and a modified polysilazane, and the modified polysilazane is applied with a coating solution containing polysilazane. sealing method for an electronic device according to any one of claims 7 to claim 9, characterized in that formed by irradiating vacuum ultraviolet light.

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