JP5139153B2 - Gas barrier film and organic device using the same - Google Patents

Description

  The present invention relates to a gas barrier film excellent in water vapor barrier properties and an organic device using the same.

  Conventionally, a film used for an organic device has been studied. For example, Patent Document 1 discloses a film for organic devices having a coating on the surface of a polymer film, wherein the coating is made of an inorganic polymer composed of silicon, nitrogen, hydrogen, and oxygen. ing. Patent Document 2 discloses a gas barrier low moisture-permeable insulation characterized by laminating a transparent thin film made of at least one nitride and a transparent thin film made of at least one oxide on at least one surface of a transparent substrate. A transparent electrode substrate is disclosed.

JP 2003-51382 A JP-A-8-68990

However, as a result of investigations by the present inventors, it has been found that the film described in Patent Document 1 has a problem of high moisture permeability, that is, poor barrier properties. This is because a silazane solution is applied on the base to produce the film. On the other hand, the substrate described in Patent Document 2 cannot provide sufficient gas barrier properties. This is because sufficient barrier properties cannot be obtained with a laminate of a transparent thin film made of nitride and a transparent thin film made of oxide as described in Patent Document 2. The cause of this is thought to be that the transparent thin film made of nitride is thin, but it has been found that if the thickness of the transparent thin film made of nitride is increased, cracks are likely to be generated.
The object of the present invention is to provide a gas barrier film having a high gas barrier property.

  As a result of intensive studies by the inventor under the above-mentioned problems, both a dense silicon nitride layer having a high water vapor blocking performance and a silicon hydronitride layer having a water vapor collecting function that reacts with water vapor and denatures into SiOx. It has been found that the above-mentioned problems can be solved by providing That is, in order to achieve high gas barrier properties, it is necessary to provide a certain thickness to the dense silicon nitride layer. However, as the thickness of the silicon nitride layer increases, the possibility that pinholes and cracks are generated in the layer increases. The generation of pinholes and cracks can be improved by using a silicon oxynitride layer and by making the silicon nitride layer thinner, but problems such as a decrease in gas barrier properties remain. As a result of intensive studies by the present inventors under such circumstances, the stress applied to the silicon nitride layer is relieved by the lamination of the silicon nitride layer and the silicon hydronitride layer that is more flexible than the silicon nitride layer, It was found that it becomes difficult to break. Furthermore, the present inventors have found that the silicon hydronitride layer expresses better barrier properties by absorbing moisture that has slightly leaked from the dense silicon nitride layer, and has completed the present invention.

Specifically, it has been found that the above problems can be solved by the following means.
(1) A gas barrier film having at least one silicon hydronitride layer and at least one silicon nitride layer on the surface of a flexible support substrate.
(2) The gas barrier film according to (1), wherein the silicon hydronitride layer and the silicon nitride layer are adjacent to each other.
(3) The gas barrier film according to (2), wherein the composition between the silicon hydronitride layer and the silicon nitride layer changes continuously and does not have a clear interface.
(4) The gas barrier film as described in any one of (1) to (3), wherein the silicon nitride layer contains silicon oxynitride.
(5) The gas-barrier film as described in any one of (1) to (4), wherein the silicon hydronitride layer contains silicon hydrogen oxynitride.
(6) Any one of (1) to (5), wherein the nitrogen content in the silicon hydronitride layer excluding silicon is 45 mol% or less and the hydrogen content is 30 mol% or more. 2. A gas barrier film according to item 1.
(7) The gas barrier film according to any one of (1) to (6), wherein the silicon hydronitride layer has a thickness of 50 to 300 nm in the gas barrier film.
(8) The gas barrier film according to any one of (1) to (7), wherein the silicon nitride layer has a thickness of 10 to 300 nm in the gas barrier film.
(9) The gas barrier film according to any one of (1) to (8), wherein the gas barrier film has at least one organic layer.
(10) The gas barrier film according to (9), wherein the organic layer contains at least one of a bifunctional acrylate and a trifunctional acrylate.
(11) The gas barrier film according to (9) or (10), wherein the organic layer is formed by curing a composition containing at least one of bifunctional methacrylate and trifunctional methacrylate.
(12) The gas barrier according to any one of (9) to (11), wherein in the gas barrier film, the organic layer is obtained by curing a composition containing at least one bisphenol-based (meth) acrylate. Sex film.
(13) The gas barrier film according to any one of (1) to (12), wherein the flexible support substrate used in the gas barrier film is polyester.
(14) An organic device using the gas barrier film according to any one of (1) to (13).
(15) An organic device sealed with the gas barrier film according to any one of (1) to (13).
(16) In an organic device manufactured by laminating an organic device material on a substrate surface, the substrate is the gas barrier film according to any one of (1) to (13), and the inorganic layer of the substrate An organic device manufactured by laminating an organic device material on the surface on which the film is formed.
(17) The organic device is any one of an organic electroluminescence display device, a liquid crystal amorphous device, a touch panel, and a solar cell conversion element, described in any one of (14) to (16) Organic devices.

  The present invention makes it possible to obtain a gas barrier film having higher water vapor barrier performance. Furthermore, it has become possible to obtain a gas barrier film having excellent bending resistance.

  Hereinafter, the gas barrier film and the organic device of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

《Gas barrier film》
(Configuration of gas barrier film)
The gas barrier film of the present invention is a film having at least one silicon hydronitride layer and at least one silicon nitride layer on a flexible support substrate (for example, a plastic film).
Thus, by having a structure having both a silicon hydronitride layer and a silicon nitride layer, it is possible to obtain a gas barrier film having excellent flex resistance while maintaining high gas barrier properties.
In the gas barrier film of the present invention, the silicon hydronitride layer and the silicon nitride layer may be adjacent to each other, and other layers (an organic layer, a layer made of an inorganic compound, a functional layer, etc.) are provided therebetween. It may be. Further, the layer may be a layer in which the composition between the silicon hydronitride layer and the silicon nitride layer continuously changes and does not have a clear interface (hereinafter, also referred to as “hydrogen composition change layer”). Naturally, a configuration including at least one of a hydrogenated silicon nitride layer and a silicon nitride layer and a hydrogen composition change layer may be employed.
The gas barrier film of the present invention is not particularly defined as long as the silicon hydronitride layer and the silicon nitride layer are provided on the substrate, but preferably one or more layers are provided on the substrate. The organic layer and one or more inorganic layers are preferably laminated. Here, the inorganic layer refers to a layer made of other inorganic compounds, a laminate thereof, and the like in addition to the silicon hydronitride layer, the silicon nitride layer, and the hydrogen composition change layer.
The gas barrier film of the present invention may be laminated in the order of the inorganic layer and the organic layer from the flexible support substrate side, or may be laminated in the order of the organic layer and the inorganic layer. The uppermost layer may be an inorganic layer or an organic layer, and may further have a functional layer thereon.
Furthermore, the gas barrier film of the present invention may be provided with an organic layer and an inorganic layer on one side of the flexible support substrate, or may be provided on both sides. When provided on both surfaces, the layer structure formed on each surface may be the same as or different from each other. As the inorganic layer on at least one surface, a silicon hydronitride layer and a silicon nitride layer Should just be provided.
Below, a preferable layer structure as a gas barrier film of this invention is shown below.
(1) Flexible support substrate / organic layer / inorganic layer (silicon nitride layer / hydrogenated silicon nitride layer / silicon nitride layer)
(2) Flexible support substrate / organic layer / inorganic layer (silicon nitride layer / hydrogen composition change layer / hydrogenated silicon nitride layer / hydrogen composition change layer / silicon nitride layer)
(3) Flexible support substrate / organic layer / inorganic layer (silicon nitride layer) / organic layer / inorganic layer (silicon nitride layer) / organic layer / inorganic layer (hydrogenated silicon nitride layer) / organic layer / inorganic layer ( (Silicon nitride layer)

(Silicon nitride layer)
The “silicon nitride layer” in the present invention refers to a layer mainly composed of silicon nitride, for example, a layer in which 90% or more by weight concentration is silicon nitride. The silicon nitride may be silicon oxynitride. By employing silicon oxynitride, flexibility and transparency become higher, which is preferable.
The silicon nitride layer preferably has a nitrogen content in the component excluding silicon of 50 mol% or more. By setting it as such a range, there exists an advantage that the layer which is dense and has high gas-barrier property, and was excellent in flexibility and transparency can be obtained.
The silicon nitride layer may contain other components, and examples thereof include aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, magnesium oxide, and the like.
The thickness of the silicon nitride layer is preferably 10 to 300 nm, and more preferably 30 to 100 nm.
Any method can be used for forming the silicon nitride layer as long as the target layer can be formed. As the formation method, for example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method and the like are suitable. Specifically, Japanese Patent Registration No. 3430344, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-322561. The formation method described in 2002-361774 gazette etc. is employable.

(Hydrosilicon nitride layer)
The “silicon hydronitride layer” in the present invention refers to a layer mainly composed of silicon hydronitride, for example, a layer in which 90% or more by weight% concentration is silicon hydronitride. The hydrogenated silicon nitride may be hydrogenated silicon oxynitride. By employing silicon oxynitride, a silicon hydride nitride layer with higher flexibility and transparency can be formed.
In the hydrogenated silicon nitride layer, the nitrogen content in the component excluding silicon is preferably 45 mol% or less, and preferably 30 mol% or less. The lower limit of the nitrogen content in the components excluding silicon is preferably 10 mol% or more, and more preferably 15 mol% or more. The hydrogenated silicon nitride layer preferably has a hydrogen content in components other than silicon of 30 mol% or more, more preferably 40 mol% or more. The upper limit of the hydrogen content is preferably 60 mol% or less, and more preferably 55 mol% or less. By setting it as such a range, there exists an advantage that water vapor | steam adsorption property becomes high.
The silicon hydronitride layer may contain other components, such as aluminum oxide, aluminum nitride, aluminum oxynitride, titanium oxide, magnesium oxide, and the like.
The thickness of the silicon hydronitride layer is preferably 50 to 300 nm, and more preferably 100 to 200 nm.
The silicon hydronitride layer can be formed by a method similar to that for the silicon nitride layer.

(Hydrogen composition change layer)
In the present invention, the silicon nitride layer and the hydrogenated silicon nitride layer may be provided as completely separate layers, but the composition between the hydrogenated silicon nitride layer and the silicon nitride layer changes continuously, and the A hydrogen composition changing layer having no interface may be used. By providing such a hydrogen composition change layer, there is an advantage that interfacial peeling is less likely to occur and stable barrier performance against bending and the like can be obtained.
The hydrogen composition change layer can be formed by adopting a method similar to that of the silicon nitride layer and continuously forming layers having different compositions. Here, continuously providing, for example, in the case of the CVD method, a gas containing a constituent material of the silicon nitride layer is introduced, and a gas to be introduced while maintaining the plasma generation state without stopping the power supply as it is, It can be formed by changing to a gas containing the constituent material of the silicon hydronitride layer and gradually shifting to discharge conditions suitable for forming the silicon hydronitride layer.

(Other inorganic layers)
The other inorganic layer in the present invention means a layer that is a thin film having a dense structure capable of suppressing the permeation of gas molecules composed of an inorganic material, and includes, for example, a thin film made of a metal compound (metal compound thin film). It is done.
The component constituting the inorganic layer is not particularly limited as long as it satisfies the above performance. For example, 1 selected from the group consisting of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like. An oxide, nitride or oxynitride containing at least one kind of metal can be used, and preferably selected from at least one metal selected from the group consisting of Si, Al, In, Sn, Ti and Zn. .
Since the inorganic layer is a thin film having a dense structure capable of suppressing the permeation of gas molecules, the film density of the thin film is preferably in the range of 2.6 g / m ^{3 to} 7.0 g / cm ³ . and more preferably in the range of ^{6g / cm 3 ~6.0g / cm 3} . The measurement of the film density of the thin film can be calculated, for example, from the X-ray reflectivity measurement of the thin film formed on the Si wafer.

(Plastic support substrate)
The gas barrier film in the present invention usually uses a plastic film as the plastic support substrate. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specifically, as the plastic film, metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin , Polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin Examples thereof include thermoplastic resins such as filn copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the gas barrier film of the present invention is used as a substrate of a device such as an organic EL element described later, the plastic film is preferably made of a material having heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate ( PAr: 210 ° C., polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Japanese Patent Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the gas barrier film of the present invention is used in combination with a polarizing plate, it is preferable that the gas barrier film is disposed so that the barrier laminate of the gas barrier film faces the inside of the cell and is located on the innermost side (adjacent to the element). At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a plastic support substrate having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate) + A linear polarizing plate is used in combination with a gas barrier film using a plastic support substrate having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate. Is preferred.

As a plastic support substrate having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR ( Co., Ltd .: Arton, Nippon Zeon Co., Ltd .: Zeonoa), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd.) U100 Pellets)), transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

Since the gas barrier film of the present invention is used as a device such as an organic EL element, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90%. That's it. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the gas barrier film of the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The thickness of the plastic film used for the gas barrier film of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

(Organic layer)
In the present invention, the organic layer is an acrylic resin or methacrylic resin, polyester, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane. , Polymer compounds such as polyether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, and fluorene ring-modified polyester. A preferable high molecular compound of the organic layer is an acrylic resin or a methacrylic resin mainly composed of a polymer of acrylate and / or methacrylate monomers. In the present invention, the polymer of the monomer mixture is obtained by polymerizing the monomer mixture. The constitution of the monomer mixture in the present invention is as follows. In the monomer mixture of the present invention, 75 to 95% by mass is a bifunctional or trifunctional acrylate or methacrylate monomer (main monomer), and 5 to 25% by mass is an acrylate or methacrylate monomer (polyfunctional monomer) having 4 or more functions. is there. The monomer mixture may contain 20% by mass or less of a monofunctional acrylate or methacrylate monomer (monofunctional monomer).
The main monomer and polyfunctional monomer in the present invention may be single or a mixture of two or more. When a monofunctional monomer is included, the monofunctional monomer may be a single type or a mixture of two or more types.

The main monomer preferably used in the present invention is a monomer represented by the following general formula (2).
General formula (2) (Ac-O) _n -L
In general formula (2), Ac represents an acryloyl group or a methacryloyl group, O represents an oxygen atom, L represents a divalent or trivalent linking group having 3 to 18 carbon atoms, and n represents 2 or 3.

The divalent linking group having 3 to 18 carbon atoms represented by L is an alkylene group (for example, 1,3-propylene, 2,2-dimethyl-1,3-propylene, 2-butyl-2-ethyl-1 , 3-propylene, 1,6-hexylene, 1,9-nonylene, 1,12-dodecylene, 1,16-hexadecylene, etc.), ether groups, imino groups, carbonyl groups, groups having a bisphenol skeleton, and these 2 A divalent residue (for example, polyethyleneoxy, polypropyleneoxy, propionyloxyethylene, butyroyloxypropylene, caproyloxyethylene, caproyloxybutylene, etc.) in which a plurality of valent groups are bonded in series.
L may have a substituent. Examples of substituents that can substitute L include alkyl groups (methyl group, ethyl group, butyl group, etc.), aryl groups (phenyl group, etc.), amino groups (for example, amino group, methylamino group, dimethylamino). Group, diethylamino group etc.), alkoxy group (eg methoxy group, ethoxy group, butoxy group, 2-ethylhexyloxy group etc.), acyl group (eg acetyl group, benzoyl group, formyl group, pivaloyl group etc.), alkoxy Examples thereof include a carbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), a hydroxy group, a halogen atom (for example, fluorine, chlorine, bromine, iodine), and a cyano group. The substituent is preferably an alkyl group or an alkoxy group.
The trivalent linking group having 3 to 18 carbon atoms represented by L is a trivalent residue obtained by removing one hydrogen atom from the above divalent linking group, or the above divalent linking group. A trivalent residue obtained by removing one arbitrary hydrogen atom from a linking group and substituting an alkylene group, an ether group, a carbonyl group, and a divalent group in which these are bonded in series.

Hereinafter, although the specific example of the main monomer represented by General formula (2) is shown, this invention is not limited to these.

The polyfunctional monomer that can be used in the present invention is not particularly limited as long as it is a tetrafunctional or higher acrylate or methacrylate monomer, but is typically a 4-6 functional acrylate or methacrylate monomer. Examples of preferred skeletons include pentaerythritol skeleton and dipentaerythritol skeleton.
Hereinafter, although the specific example of the preferable polyfunctional monomer which can be used for this invention is shown, this invention is not limited to these.

  The monofunctional monomer that can be used in the present invention is not particularly limited as long as it is an acrylate or methacrylate monomer, but is typically an acrylate or methacrylate monomer having a molecular weight of 150 to 600. Although the preferable specific example of the monofunctional monomer which can be used for this invention below is shown, this invention is not limited to these.

  Examples of the method for forming the organic layer include a normal solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, and a gravure coating method. It can be applied by the slide coating method or the extrusion coating method using a hopper described in US Pat. No. 2,681,294. Although there is no restriction | limiting in particular as a vacuum film-forming method, The flash vapor deposition method as described in US Patent 4,842,893, 4954371, 5032461 is preferable.

The monomer polymerization method is not particularly limited, but heat polymerization, light (ultraviolet ray, visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination thereof is preferably used. Of these, photopolymerization is particularly preferred. When carrying out photopolymerization, a photopolymerization initiator is used in combination. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959 Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc., commercially available from Ciba Specialty Chemicals. ), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, etc.) commercially available from Sartomer. Can be mentioned.
The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more. Since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

The film thickness of the organic layer is not particularly limited, but if it is too thin, it is difficult to obtain film thickness uniformity. If it is too thick, the amount of moisture entering from the side surface increases, and the barrier property decreases. From this viewpoint, the thickness of the adjacent organic layer is preferably 50 nm to 2000 nm, and more preferably 200 nm to 1500 nm.
It is desirable that the organic layer thus installed is smooth. The smoothness of the organic layer is preferably 10 nm or less, more preferably 5 nm or less, and particularly preferably 2 nm or less as the Ra value as measured by AFM.
The organic layer is preferably provided on both sides of the inorganic layer in a state adjacent to the inorganic layer. By adopting such means, a gas barrier film that is more resistant to bending can be obtained.

《Organic device》
The organic device of the present invention refers to, for example, an image display element (circular polarizing plate / liquid crystal display element, electronic paper or organic EL element), a dye-sensitized solar cell, a touch panel, and the like. Although the use of the gas barrier film of the present invention is not particularly limited, it can be suitably used as a substrate or a sealing film of the organic device.

<Circularly polarizing plate>
The circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on the gas barrier film of the present invention. In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

<Liquid crystal display element>
The liquid crystal display device can be roughly classified into a reflective liquid crystal display device and a transmissive liquid crystal display device. The reflective liquid crystal display device includes a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film of the present invention can be used as the transparent electrode and the upper substrate. When the reflective liquid crystal display device has a color display function, a color filter layer may be further provided between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. preferable.

  Further, the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, and λ / 4. It has the structure which consists of a board and a polarizing film. Among these, the gas barrier film of the present invention can be used as the upper transparent electrode and the upper substrate. Further, when the transmissive liquid crystal display device has a color display function, a color filter layer is further provided between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. It is preferable to provide it.

  The structure of the liquid crystal layer is not particularly limited. For example, a TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB (Electrically Controlled Birefringence) type An OCB (Optically Compensated Bend) type, an IPS type (In-Plane Switching) type, or a CPA (Continuous Pinwheel Alignment) type is preferable.

(Touch panel)
As the touch panel, a substrate in which the gas barrier film of the present invention is applied to a substrate described in JP-A Nos. 5-127822 and 2002-48913 can be used.

(Organic EL device)
The organic EL device of the present invention has a cathode and an anode on a substrate, and has an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.
(anode)
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element, but it is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof. The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method. The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more. The transparent anode is described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

(cathode)
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say. The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like. Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof. Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by forming a thin film of the cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(Organic compound layer)
The organic compound layer in the present invention will be described.
The organic electroluminescent element of the present invention has at least one organic compound layer including a light emitting layer, and the organic compound layer other than the organic light emitting layer includes a hole transport layer, an electron transport layer as described above. , Charge blocking layer, hole injection layer, electron injection layer and the like.

(Formation of organic compound layer)
In the organic electroluminescent element of the present invention, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.
(Organic light emitting layer)
The organic light emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer having a function of providing a field to emit light. The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent light-emitting materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and pyromethene derivatives And various metal complexes typified by metal complex, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

  Examples of the phosphorescent material that can be used in the present invention include complexes containing transition metal atoms or lanthanoid atoms. Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum. Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

  Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha. Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass. Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later. Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

(Hole injection layer, hole transport layer)
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon And the like. The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.

  The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

(Electron injection layer, electron transport layer)
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

  The thicknesses of the electron injection layer and the electron transport layer are each preferably 50 nm or less from the viewpoint of lowering the driving voltage. The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(Hole blocking layer)
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(Protective layer)
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, a material having a planarizing action and a material having a function of preventing moisture and oxygen from entering the element are preferable. Specific examples, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni, MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 O 3 , Y ₂ O _3, TiO ₂ and metal oxides, metal nitrides such as SiN _x, SiN _x O _y or the like of metallic _{oxynitride, MgF 2, LiF, AlF 3} , CaF 2 , etc. of the metal fluoride, polyethylene , Polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerizing a monomer mixture containing a cyclic structure in the copolymer main chain Fluorine-containing copolymer having 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like. Of these, metal oxides, nitrides, and nitride oxides are preferable, and silicon oxides, nitrides, and nitride oxides are particularly preferable.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, vacuum ultraviolet CVD method, coating method, printing method, transfer method can be applied. In the present invention, a protective layer may be used as the conductive layer.

(Sealing)
Furthermore, the organic electroluminescent element of this invention may seal the whole element using a sealing container. Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

  As another sealing method, a so-called solid sealing method may be used. The solid sealing method is a method in which a protective layer is formed on an organic EL element, and then an adhesive layer and a barrier support layer are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated. The barrier support may be glass or the barrier film of the present invention.

  As another sealing method, a so-called film sealing method may be used. The film sealing method is a method of providing an alternating laminate of an inorganic layer and an organic layer on an organic EL element. The organic EL element may be covered with a protective layer before providing the alternate laminate.

  The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Can be obtained. The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Reference Example 1 Production and Evaluation of Gas Barrier Film A gas barrier film having the layer structure shown in FIG. 1 was produced. In FIG. 1, 1 is a polyethylene naphthalate film, 2 is an organic layer, 3-1 and 3-2 are silicon nitride layers, and 4 is a hydrogenated silicon nitride layer.

(1-1 Preparation of support)
A polyethylene naphthalate film (PEN film, manufactured by Teijin DuPont, trade name: Teonex Q65FA) was used as a support. An organic layer was formed on one side of the support by the following method.

(1-2 Formation of organic layer)
On one side of the support, an organic layer coating solution having the following composition was applied by a bar coating method. The coating amount was 5 cc / m ^2, and the organic layer was irradiated with ultraviolet rays from a high-pressure mercury lamp (accumulated irradiation amount: about ² J / cm ² ) in a chamber in which the oxygen concentration became 0.1% or less by the nitrogen substitution method. It was made by curing.
<Organic layer coating solution>
・ Acrylate monomer; BEPGA 20g
・ Ultraviolet polymerization initiator: Irgacure 907 (Ciba Specialty) 0.6g
・ 2-butanone 190g
The film thickness at this time was 500 nm ± 50 nm.

(1-3 Formation of inorganic layer)
An inorganic layer (a silicon nitride layer, a hydrogenated silicon nitride layer, and a silicon nitride layer) was formed on the surface of the organic layer formed above by plasma CVD.
A substrate coated with an organic layer is set in a reaction chamber, and under reduced pressure, a raw material gas according to the plasma CVD raw material gas formulation 1 described below is introduced, and a high frequency power of 13.56 MHz is supplied for a certain period of time. A silicon nitride layer (N component excluding Si: 97 mol%) was formed. The thickness was set to 50 nm. Next, a source gas in accordance with the plasma CVD source gas formulation 2 was introduced, and a silicon hydronitride layer (N component excluding Si: 36 mol%, H component: 63 mol%) was formed in the same manner. The thickness was set to 100 nm. Further, a source gas according to the plasma CVD source gas formulation 1 described below was introduced again to form a silicon nitride layer (N component excluding Si: 97 mol%). The thickness was set to 50 nm. The plasma was stopped once for each layer formation.
The total thickness of the inorganic layers in this reference example was 200 nm ± 10 nm.

<Plasma CVD source gas prescription 1>
Silane gas 25sccm
Ammonia gas 15sccm
Nitrogen gas 200sccm
<Plasma CVD source gas prescription 2>
Silane gas 25sccm
Ammonia gas 50sccm
Nitrogen gas 165sccm

Example 1
A gas barrier film having the layer structure shown in FIG. 2 was produced. In FIG. 2, 1 is a polyethylene naphthalate film, 2 is an organic layer, 3-1 and 3-2 are silicon nitride layers, 4 is a hydrogenated silicon nitride layer, and 5-1 and 5-2 are hydrogen flow rates. The hydrogen composition change layer formed at the time of a change is shown, respectively.

In the same manner as in Reference Example 1, an organic layer and a silicon nitride layer (N component excluding Si: 97 mol%) were formed on the support.
On top of this, a gas according to the plasma CVD source gas formulation 1 used in Reference Example 1 was introduced for a time required to form a silicon nitride layer having a thickness of about 50 nm. Next, the gas to be introduced was changed to the gas according to the plasma CVD source gas prescription 2 used in Reference Example 1 while maintaining the plasma generation state without stopping the power supply. A gas according to the plasma CVD source gas recipe 2 was introduced for a time required to form a silicon hydronitride layer having a thickness of about 100 nm. Then, the gas according to the plasma CVD source gas prescription 1 was introduced while maintaining the plasma generation state without stopping the power supply. A gas in accordance with the plasma CVD source gas prescription 1 was introduced until a time for forming a silicon nitride layer having a thickness of about 50 nm was formed, and then the power supply was stopped to produce a hydrogen composition change layer. .
In this example, the total thickness of the inorganic layers was 200 nm ± 10 nm.

Example 2
A gas barrier film having the layer structure shown in FIG. 3 was produced. In FIG. 3, 1 is a polyethylene naphthalate film, 2-1, 2-2, 2-3 are organic layers, 3-1 and 3-2 are silicon nitride layers, and 4 is a silicon hydronitride layer. Show.
In accordance with the method described in Reference Example 1 and Example 1 , the support, the organic layer, the silicon nitride layer (thickness of 50 nm, N component excluding Si: 97 mol%), the organic layer, the silicon hydronitride layer (thickness of 150 nm) N component excluding Si: 36 mol%, H component: 63 mol%), organic layer, silicon nitride layer (50 nm thickness, N component excluding Si: 97 mol%) were prepared.

Reference example 2
In Reference Example 1, the acrylate monomer in the organic layer was replaced with 20 g of the following compound, and the others were performed in the same manner.

Comparative Example 1
A gas barrier film having the layer structure shown in FIG. 4 was produced. In FIG. 4, 1 is a polyethylene naphthalate film, 2 is an organic layer, and 3 is a silicon nitride layer.
In accordance with the method described in Reference Example 1 and Example 1 , a support, an organic layer, and a silicon nitride layer (thickness of 200 nm, N component excluding Si: 97 mol%) were prepared in this order.

Water Vapor Barrier Performance Evaluation Test The water vapor transmission rate at 40 ° C. and 90% relative humidity of each gas barrier film produced in Reference Examples 1 and 2, Examples 1 and 2 and Comparative Example 1 was measured using a water vapor transmission rate meter (MOCON). Manufactured by PERMATRAN-W3 / 31). The detection limit of this measurement is 0.005 g / m ² / day.
When each gas barrier film was measured without being bent, Table 1 shows the respective results when measured after repeatedly bending 100 times with a radius of curvature of 20 mm (20 mmR). The gas barrier film was bent by a cylindrical mandrel method (JIS K5600-5-1).

As is apparent from Table 1 above, the laminated structure having the silicon nitride layer and the silicon hydronitride layer has higher water vapor barrier performance and bending resistance than the conventionally proposed gas barrier film. It was revealed that a gas barrier film having excellent properties can be obtained. In particular, in Example 1 , as a result of successively forming a hydrogen composition change layer, a silicon hydronitride layer, and a hydrogen composition change layer, a gas barrier film stronger by bending than that of Reference Example 1 was obtained. Further, in Example 2 , by providing a plurality of organic layers, these layers acted as stress relaxation layers, and a gas barrier film stronger by bending than that of Reference Example 1 was obtained.

Example 3 Preparation and Evaluation of Organic EL Element (2-1) Preparation of Organic EL Element A conductive glass substrate having an ITO film (surface resistance value 10Ω / □) was washed with 2-propanol, and then UV-for 10 minutes. Ozone treatment was performed. The following layers were sequentially deposited on this substrate (anode) by vacuum deposition.
(First hole transport layer)
Copper phthalocyanine film thickness 10nm
(Second hole transport layer)
N, N'-diphenyl-N, N'-dinaphthylbenzidine film thickness 40nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum film thickness 60nm
Finally, 1 nm of lithium fluoride and 100 nm of metal aluminum were sequentially deposited to form a cathode, and a 5 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL device.

(2-2) Installation of Gas Barrier Layer on Organic EL Element The gas barrier film of Reference Example 1 or Example 1 is bonded using a thermosetting adhesive (Epotech 310, manufactured by Daizonichi Mori Co., Ltd.). The adhesive was cured by heating at 65 ° C. for 3 hours. 20 organic EL elements sealed in this way were produced.

(2-3) Evaluation of light emitting surface state of organic EL element The organic EL element immediately after production was made to emit light by applying a voltage of 7 V using a SMU2400 type source measure unit manufactured by Keithley. When the surface of the light emitting surface was observed using a microscope, it was confirmed that all the elements gave uniform light emission without dark spots. In addition, it was confirmed that any element gave uniform light emission without dark spots even after 500 hours had passed in an environment of 60 ° C./90° C. RH.

  The gas barrier film of the present invention has an extremely high water vapor barrier property. Moreover, the gas barrier film of the present invention can maintain a high water vapor barrier property even when bent. Therefore, the gas barrier film of the present invention can be effectively used for a wide range of applications including flexible organic EL devices.

FIG. 1 shows the layer structure of the gas barrier film produced in Reference Example 1. FIG. 2 shows the layer structure of the gas barrier film produced in Example 1 . FIG. 3 shows the layer structure of the gas barrier film produced in Example 2 . FIG. 4 shows the layer structure of the gas barrier film produced in Reference Example 2 .

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyethylene naphthalate film 2 Organic layer 2-1 Organic layer 2-2 Organic layer 2-3 Organic layer 3 Silicon nitride layer 3-1 Silicon nitride layer 3-2 Silicon nitride layer 4 Hydrogenated silicon nitride layer 5-1 Hydrogen composition Change layer 5-1 Hydrogen composition change layer

Claims (15)

Flexible support and have at least one layer silicon hydronitride layer and at least one layer of silicon nitride layer on the surface of the substrate, at least one layer of at least one layer and said silicon nitride layer of the hydrogenated silicon nitride layer A gas barrier film characterized in that they are adjacent and the composition between these adjacent layers is continuously changing and does not have a clear interface . The gas barrier film according to claim 1 , wherein the silicon nitride layer contains silicon oxynitride. The gas barrier film according to claim 1 or 2 , wherein the silicon hydronitride layer contains hydrogenated silicon oxynitride. According to any one of claims 1 to 3, wherein the partial nitrogen of the ingredients except silicon in the silicon hydronitride layer is 45 mol% or less and and hydrogen partial is 30 mol% or more Gas barrier film. Wherein the gas barrier film, the film thickness of the silicon hydronitride layer, gas barrier film according to claim 1 any one of 4, which is a 50 to 300 nm. The gas barrier film according to any one of claims 1 to 5 , wherein in the gas barrier film, the silicon nitride layer has a thickness of 10 to 300 nm. Wherein the gas barrier film, gas barrier film according to any one of claims 1 to 6, characterized in that it comprises at least one organic layer. The gas barrier film according to claim 7 , wherein in the gas barrier film, the organic layer is formed by curing a composition containing at least one of a bifunctional acrylate and a trifunctional acrylate. The gas barrier film according to claim 7 or 8 , wherein in the gas barrier film, the organic layer contains at least one of bifunctional methacrylate and trifunctional methacrylate. The gas barrier film according to any one of claims 7 to 9 , wherein in the gas barrier film, the organic layer is formed by curing a composition containing at least one bisphenol-based (meth) acrylate. Gas barrier film according to any one of claims 1 to 10 in the gas barrier film, the flexible supporting substrate used is characterized in that it is a polyester. An organic device using the gas barrier film according to any one of claims 1 to 11 . The organic device, characterized in that sealed with the gas barrier film according to any one of claims 1 to 11. In the organic device manufactured by laminating the organic device material on the substrate surface, the substrate is the gas barrier film according to any one of claims 1 to 11 , and the inorganic layer of the substrate is formed. An organic device manufactured by laminating an organic device material on a side surface. The organic device according to any one of claims 12 to 14 , wherein the organic device is any one of an organic electroluminescence display device, a liquid crystal amorphous device, a touch panel, and a solar cell conversion element.

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