JP4717497B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a film excellent in gas barrier properties, and particularly relates to a laminated gas barrier film suitable for substrates and coating films of various organic devices. Furthermore, the present invention relates to an organic device excellent in durability and flexibility, particularly an organic EL element, using the gas barrier film.

In recent years, in organic devices such as liquid crystal display elements, solar cells, and electroluminescence (EL) elements, it has been studied to use a thin, light, and flexible plastic film as a substrate instead of a heavy and fragile glass substrate. ing. The transparent plastic substrate is also advantageous in terms of productivity and cost reduction compared to glass because it can easily be increased in area and can be applied to a roll-to-roll production method.
However, the transparent plastic film has a problem that the gas barrier property is inferior to that of glass. In general, organic devices are likely to be deteriorated or altered by water or air in the constituent materials. For example, when a base material having inferior gas barrier properties is used for the substrate of the liquid crystal display element, the liquid crystal in the liquid crystal cell is deteriorated, and the deteriorated portion becomes a display defect and deteriorates the display quality.

In order to solve such a problem, the above-described plastic film substrate itself may be provided with a gas barrier function, or the entire device may be sealed with a transparent plastic film having gas barrier properties. In general, a metal oxide thin film formed on a plastic film is known as a gas barrier film. For example, as a gas barrier film used for a liquid crystal display element, there are a film in which silicon oxide is vapor-deposited on a plastic film (see Patent Document 1) and a film in which aluminum oxide is vapor-deposited (see Patent Document 2). All of these have a water vapor barrier property of about 1 g / m ² / day. However, in recent years, organic EL displays and high-definition color liquid crystal displays that require higher barrier properties have been developed, maintaining transparency that can be used for them, and having high barrier properties, particularly water vapor barrier properties. A substrate having a performance of less than 1 g / m ² / day has been required.

  In order to meet such demands, as a means for expecting higher barrier performance, studies are being made on film formation by sputtering or CVD, in which a thin film is formed using plasma generated by glow discharge under low pressure conditions. In addition, a technique has been proposed in which a barrier film having an alternately laminated structure of organic layers / inorganic layers is manufactured by vacuum deposition (see Patent Document 3 and Non-Patent Document 1).

On the other hand, when a transparent plastic substrate is used for an organic device, an ultraviolet blocking function is required in addition to a barrier function for various gases. For example, ultraviolet light emitted from a self-luminous element (such as EL) causes deterioration of the plastic substrate and accelerates deterioration of the element. Moreover, the ultraviolet rays from external light cause deterioration and alteration of not only the plastic substrate but also the device material. In order to solve such a problem, development of a plastic film having a gas barrier property and an ultraviolet blocking function has been studied. For example, a gas barrier film coated with a titanium oxide layer is known. In this case, the titanium oxide layer not only absorbs ultraviolet rays but also has a photocatalytic function. It may not be possible (Patent Document 4). Further, the gas barrier property is not sufficient. For this reason, development of a plastic film having both a high gas barrier property and a function of stably blocking ultraviolet rays has been desired.
Japanese Patent Publication No.53-12,953 (pages 1 to 3) JP 58-217,344 A (pages 1 to 4) US Pat. No. 6,413,645 B1 (page 4 [2-54] to page 8 [8-22]) JP 2004-338201 A (pages 1 to 16) “Thin Solid Films” (1996), Affinito et al. 290-291 (pages 63-67)

  In order to solve the above-mentioned problems, the present invention aims to provide a plastic film having high barrier properties and transparency, and also having an ultraviolet blocking function, and further using this film for a long period of time. An object of the present invention is to provide an organic device (for example, an organic EL element or a dye-sensitized solar cell) that hardly deteriorates even when used.

The above problem can be solved by the following means.
[1] A gas barrier film in which a gas barrier layer composed of at least one layer of an inorganic compound is formed on a transparent flexible support substrate, and the water vapor permeability at 40 ° C. and 90% relative humidity of the film is 0.00. A gas barrier film having a transmittance of 005 g / m ² / day or less and an ultraviolet ray transmittance of 350 nm or less of 10% or less.
[2] The gas barrier film according to [1], wherein the inorganic compound constituting the gas barrier layer contains a metal oxide as a main component.
[3] The inorganic compound constituting the gas barrier layer is mainly composed of a compound containing at least one metal selected from the group consisting of Si, Al, In, Sn, and Zn [1] Or the gas barrier film as described in [2].
[4] The gas barrier film according to any one of [1] to [3], wherein the gas barrier film contains at least one organic ultraviolet absorber.
[5] The gas barrier film according to [4], wherein at least one ultraviolet blocking layer containing part or all of the organic ultraviolet absorber is formed on the support substrate.

[6] The gas barrier film according to [5], wherein the ultraviolet blocking layer is provided on at least one outermost surface of the gas barrier film.
[7] The gas barrier film according to [6], wherein the ultraviolet blocking layer is provided on both outermost surfaces of the gas barrier film.
[8] The gas barrier film according to [6], wherein the ultraviolet blocking layer is provided on a support substrate surface opposite to the surface on which the gas barrier layer is formed.
[9] The gas barrier film according to any one of [1] to [8], wherein the gas barrier layer and the layer made of an organic compound are alternately provided in plural layers.
[10] The gas barrier film as described in [9], wherein the layer made of the organic compound is a polymer layer formed by applying an ultraviolet curable monomer and curing with an ultraviolet ray.

[11] An organic device using the gas barrier film according to any one of [1] to [10].
[12] An organic device sealed with the gas barrier film according to any one of [1] to [10].

  The gas barrier film of the present invention has high barrier properties and transparency, and also has an ultraviolet blocking function. Further, the organic device of the present invention is hardly deteriorated even when used for a long time.

  Hereinafter, the gas barrier film having an ultraviolet blocking effect 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>
The gas barrier film of the present invention has a gas barrier layer composed of at least one inorganic compound (hereinafter sometimes referred to as an inorganic gas barrier layer) on a substrate film that is a transparent flexible support. The film of the present invention can exhibit a higher gas barrier ability by laminating an inorganic gas barrier layer and a layer composed of an organic compound (hereinafter sometimes referred to as an organic layer). Water vapor permeability at 40 ° C. · 90% relative humidity of the gas barrier film of the present invention is not more than 0.005g / m ² / day, preferably not more than 0.001g / m ² / day. The gas barrier film of the present invention achieves both high gas barrier ability and high ultraviolet shielding ability by laminating a shielding layer made of an ultraviolet compound.
In the gas barrier film of the present invention, a hygroscopic layer, an antistatic layer, a conductive layer and the like can be provided on a transparent flexible support in addition to the inorganic gas barrier layer and the ultraviolet blocking layer.

(Inorganic gas barrier layer)
The “gas barrier layer made of an inorganic compound” in the present invention means a layer that is a thin film having a dense structure capable of suppressing the permeation of gas molecules made of an inorganic material. For example, a thin film made of a metal compound (metal compound) Thin film). As the method for forming the inorganic gas barrier layer, any method can be used as long as it can form a target thin film. As the forming 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. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-2002. The formation method described in each publication of 361774 can be employed.
The component contained in the inorganic gas barrier 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, oxynitride, or the like containing more than one kind of metal can be used. Preferably, it is selected from at least one metal selected from the group consisting of Si, Al, In, Sn and Zn.

Also, the thickness of the inorganic gas barrier layer is not particularly limited, but if the thickness is too thick, there is a risk of cracking due to bending stress, and if it is too thin, the film is distributed in an island shape. is there. Therefore, the thickness of each inorganic gas barrier layer is preferably in the range of 5 nm to 1000 nm, more preferably 10 nm to 1000 nm, and most preferably 10 nm to 200 nm.
The two or more inorganic gas barrier layers may have the same composition or different compositions, and are not particularly limited.

  In the present invention, it is preferable to use silicon oxide, silicon nitride, or silicon oxynitride as the inorganic gas barrier layer in order to achieve both gas barrier properties and high transparency. When SiOx, which is a silicon oxide, is used as the inorganic gas barrier layer, it is desirable that 1.6 <x <1.9 in order to achieve both good gas barrier properties and high light transmittance. When SiNy which is silicon nitride is used as the inorganic gas barrier layer, it is preferable that 1.2 <y <1.3. When y <1.2, coloring may increase, which is a limitation when used in display applications.

  When SiOxNy, which is silicon oxynitride, is used as the inorganic gas barrier layer, it is preferable to use an oxygen-rich film if importance is placed on improving adhesion, specifically, 1 <x <2 and 0 It is preferable that <y <1 is satisfied. On the other hand, when importance is attached to the improvement of gas barrier properties, a nitrogen-rich film is preferable, and specifically, it is preferable to satisfy 0 <x <0.8 and 0.8 <y <1.3. .

(Organic layer)
In the gas barrier film of the present invention, an organic layer adjacent to each layer can be provided in order to improve the brittleness and barrier properties of the inorganic gas barrier layer. The organic layer is preferably a layer obtained by forming a film of ultraviolet or electron beam curable monomer, oligomer or resin by coating or vapor deposition and then curing the film with ultraviolet or electron beam.

The organic layer will be described by taking as an example the case of using an organic layer formed mainly of a polymer obtained by crosslinking monomers. The monomer is not particularly limited as long as it has a group that can be cross-linked by irradiation with ultraviolet rays or electron beams, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxetane group.
The organic layer includes, for example, epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester ( Among the (meth) acrylates and the like, it is preferable that the main component is a polymer obtained by crosslinking a monomer having a bifunctional or higher functional acryloyl group or methacryloyl group. These monomers having a bifunctional or higher functional acryloyl group or methacryloyl group may be used as a mixture of two or more, or may be used as a mixture of a monofunctional (meth) acrylate.

  Moreover, as a monomer which has the said oxetane group, the monomer which has the structure described in General formula (3)-(6) of Unexamined-Japanese-Patent No. 2002-356607 is mentioned suitably, for example. In this case, you may mix these arbitrarily.

  The organic layer is mainly composed of isocyanuric acid acrylate, epoxy acrylate, and urethane acrylate having a high degree of crosslinking and a glass transition temperature of 200 ° C. or higher from the viewpoint of heat resistance and solvent resistance required for display applications. More preferably, it is a component. The thickness of the organic layer is not particularly limited, but if the thickness of the organic layer is too thin, it is difficult to obtain thickness uniformity, so that structural defects of the inorganic gas barrier layer are efficiently filled with the organic layer. It is not possible to improve the barrier property. On the other hand, if the thickness of the organic layer is too thick, the organic layer is likely to crack due to an external force such as bending, resulting in a problem that the barrier property is lowered. From this viewpoint, the thickness of the organic layer is preferably 10 nm to 5000 nm, more preferably 10 nm to 2000 nm, and most preferably 50 nm to 2000 nm.

  Examples of the method for forming an organic layer of the present invention include a method in which a coating film containing a crosslinkable monomer is first formed and then the coating film is cured by irradiation with an electron beam or ultraviolet rays. Examples of the method for forming the coating film include a coating method and a vacuum film forming method. Although there is no restriction | limiting in particular as said vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable, and the resistance heating vapor deposition method which is easy to control the film-forming rate of an organic substance monomer is more preferable. There are no particular restrictions on the crosslinking method for the crosslinkable monomer or the like, but crosslinking with an electron beam or ultraviolet rays is desirable in that it can be easily mounted in a vacuum chamber and the high molecular weight by a crosslinking reaction is rapid.

When the coating film is applied by a coating method, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.
As the method for forming the coating film, either a coating method or a vapor deposition method may be used. However, a vacuum film forming method that is difficult to apply mechanical stress after forming an inorganic gas barrier layer immediately below and is advantageous for forming a thin film is used. It is preferable.

(UV blocking layer)
The gas barrier film of the present invention has an ultraviolet blocking function. Since it has the ultraviolet blocking function, it is possible to prevent the gas barrier film from being deteriorated by external light or ultraviolet rays from the self-light-emitting element. The gas barrier film of the present invention blocks ultraviolet rays having a wavelength of 350 nm to a transmittance of 10%, preferably to 5% or less. The ultraviolet blocking function can be achieved by a method of containing the following ultraviolet absorber or ultraviolet blocking agent in a substrate film or an organic layer, a method of inserting it as a separate layer, or the like. A method of adding another layer as the ultraviolet blocking layer is preferable.

  The compound that achieves the ultraviolet blocking function is not particularly limited, and examples thereof include organic ultraviolet absorbers such as thiazolidone-based, benzotriazole-based, acrylonitrile-based, benzophenone-based, aminobutadiene-based, and triazine-based compounds, or cerium oxide and magnesium oxide. In particular, an organic ultraviolet absorber is preferable. Examples of the organic ultraviolet absorber include JP-A-46-3335, JP-A-55-15276, JP-A-5-197704, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent Nos. 711804A and 8-501291, U.S. Pat. Nos. 1,023,859, 2,685,512, 2,739,888, and 2,784,087. No. 2,748,021, No. 3,004,896, No. 3,052,636, No. 3,215,530, No. 3,253,9 No. 1, No. 3,533,794, No. 3,692,525, No. 3,705,805, No. 3,707,375, No. 3,738,837, No. The compounds described in 3,754,919, British Patent 1,321,355 and the like can be used.

  When an ultraviolet blocking layer is added, the ultraviolet absorbing agent or ultraviolet blocking agent is dispersed in an organic binder to form a layer. The organic binder is not particularly limited, but synthetic resins can be used. Examples of the method for forming the ultraviolet blocking layer include a coating method. When the coating film is applied by a coating method, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used. Although the said ultraviolet absorber or ultraviolet blocker in this coating liquid contains an appropriate quantity when adjusting an ultraviolet-ray transmittance, Preferably it is 0.1-50 mass%, More preferably, it is 1-30 mass. %.

  The thickness of the ultraviolet blocking layer of the present invention is preferably 10 nm to 5000 nm, more preferably 50 nm to 5000 nm, and most preferably 100 nm to 5000 nm. The ultraviolet blocking layer may be disposed at any position between the substrate film, the inorganic gas barrier layer, and the organic layer, but is preferably on the outermost surface of at least one of the gas barrier films of the present invention, It is preferable to be on the outermost surface opposite to the surface on the support substrate on which the inorganic gas barrier layer is formed. Moreover, the aspect which has this ultraviolet-ray blocking layer in both surfaces of the outermost surface of a gas barrier film is also preferable.

(Substrate film)
If the board | substrate film used for the gas barrier film of this invention is a film which can hold | maintain each said layer, there will be no restriction | limiting in particular, According to the intended purpose etc., it can select suitably. Specific examples of the substrate film substrate include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, Ether imide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified carbonate resin, Examples thereof include thermoplastic resins such as alicyclic modified polycarbonate resins and acryloyl compounds. Among these resins, preferred examples include polyester resins such as polyethyl naphthalate resin (PEN), polyarylate resin (PAr), polyethersulfone resin (PES), and fluorene ring-modified carbonate resin (BCF-PC: JP Example -4 of JP-A 2000-227603), alicyclic modified polycarbonate resin (IP-PC: compound of Example -5 of JP-A 2000-227603), acryloyl compound (JP-A 2002-80616) The film which consists of compounds, such as the compound of Example-1 of these, is mentioned.
The substrate film used in the present invention is transparent to visible light because it is used as a support for organic devices. The transparency of the substrate film is preferably 50% or more of visible light having a wavelength of 500 nm. The thickness of the substrate film can be appropriately adjusted in order to ensure transparency.

(Other functional layers)
The gas barrier film of this invention can install a well-known primer layer or an inorganic thin film layer between a base film and an inorganic gas barrier layer. Examples of the primer layer include a resin layer such as an acrylic resin, an epoxy resin, a urethane resin, and a silicone resin, an organic-inorganic hybrid layer formed by a sol-gel reaction in the presence of a hydrophilic resin, an inorganic vapor deposition layer, or a dense sol-gel method. An inorganic layer can be mentioned. As said inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like. It is also preferable to insert a hygroscopic layer between the two inorganic gas barrier layers because the water vapor barrier performance is improved. In this case, the hygroscopic layer may be disposed at a position adjacent to the two inorganic gas barrier layers, a position adjacent to the inorganic gas barrier layer and the organic layer, or a position adjacent to the two organic layers. From the viewpoint of reducing the effect of deformation due to the brittleness of the layer and the volume expansion after moisture absorption, it is most desirable to be disposed between the two inorganic gas barrier layers adjacent to the two organic layers.

Furthermore, the gas barrier film of the present invention may be provided with various functional layers in addition to the inorganic gas barrier layer and the organic layer. Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and a light extraction efficiency improving layer; a mechanical functional layer such as a hard coat layer and a stress relaxation layer; an antistatic layer and a conductive layer. An electric functional layer such as: an antifogging layer; an antifouling layer; a layer to be printed, and the like. These functional layers may be disposed between any of the base film, the inorganic gas barrier layer, the ultraviolet blocking layer, and the organic layer, or on the opposite surface of the substrate film on which the inorganic gas barrier layer is disposed.
Further, a gas barrier laminate layer in which at least an inorganic gas barrier layer, an organic layer, and an inorganic gas barrier layer are laminated in this order can be provided on the opposite side of the hygroscopic layer from the base film. The gas barrier laminate layer suppresses the dimensional change of the film substrate by preventing intrusion of water molecules from the opposite side of the film, thereby preventing stress concentration and destruction to the gas barrier layer, resulting in a highly durable display. It has the feature that it can.

(Configuration of each layer)
The gas barrier film of the present invention has at least one inorganic gas barrier layer on a substrate film, and is preferably formed by laminating at least one inorganic gas barrier layer and an organic layer. A mode in which the inorganic gas barrier layer and the organic layer are laminated on both sides of the substrate film is also suitable.

《Organic device》
The organic device in 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 this invention is not specifically limited, It can use suitably as a board | substrate or sealing film of this 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.

  The transmissive liquid crystal display device includes 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 in order from the bottom. 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 (Supper Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB (Electrically Controlled Birefringence) type, for example. An OCB (Optically Compensatory Bend) 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)
Hereinafter, an “organic EL element” (hereinafter sometimes simply referred to as “light-emitting element”) will be described in detail as a representative example of the organic device in the present invention. The organic EL element has a cathode and an anode on a substrate, and 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 a lamination mode of the organic compound layer, a mode in which a hole transport layer, a light emitting layer, and an electron transport layer are stacked in this order from the anode side is preferable. Furthermore, 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. Further, the light emitting layer may be only one layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.

  Next, elements constituting the light emitting material will be described in detail.

(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 (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metals such as oxides, gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene and polypyrrole Organic conductive materials, and laminates of these with 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 light-emitting element, 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. 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.), Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum alloy, magnesium- Examples thereof include silver alloys, rare earth metals such as indium and ytterbium. 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, the material constituting the cathode is preferably an alkali metal or a Group 2 metal from the viewpoint of electron injection, 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 group 2 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 light-emitting element, 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 a fluoride or oxide of an alkali metal or a Group 2 metal 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 depositing a thin 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 light emitting element will be described.
The light-emitting element has at least one organic compound layer including a light-emitting layer, and as the organic compound layer other than the organic light-emitting layer, as described above, a hole transport layer, an electron transport layer, a charge blocking layer , Hole injection layer, electron injection layer and the like.

-Formation of organic compound layer-
In the light-emitting element, 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 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.

  In the light-emitting element, a light-emitting element of any color can be obtained by using two or three or more different light-emitting materials. Especially, the white light emitting element which is high luminous efficiency and high luminous brightness can be obtained by selecting a luminescent material appropriately. For example, white light can be emitted using a light emitting material that emits a complementary color, such as blue light emission / yellow light emission, light blue light emission / orange light emission, and green light emission / purple light emission. Further, white light can be emitted using a light emitting material of blue light emission / green light emission / red light emission. Note that the host material may function as a light emitting material to emit light. For example, the element may emit white light by light emission of the host material and light emission of the light emitting material.

  In the light emitting element, two or more different kinds of light emitting materials may be included in the same light emitting layer. For example, blue light emitting layer / green light emitting layer / red light emitting layer, or blue light emitting layer / yellow light emitting layer Thus, a structure in which layers each containing a light emitting material are stacked may be employed.

  There are the following methods for adjusting the emission color of the light emitting layer. The emission color can be adjusted using one or more of these methods.

1) A method of adjusting by providing a color filter on the light extraction side of the light emitting layer.
The color filter adjusts the emission color by limiting the wavelength to transmit. As the color filter, for example, cobalt oxide is used as a blue filter, a mixed system of cobalt oxide and chromium oxide is used as a green filter, and a known material such as iron oxide is used as a red filter. It may be formed on a transparent substrate using the thin film deposition method.

2) A method of adjusting the emission color by adding a material that promotes or inhibits light emission.
For example, a so-called assist dopant that receives energy from the host material and transfers this energy to the light emitting material can be added to facilitate energy transfer from the host material to the light emitting material. As an assist dopant, it selects from a well-known material suitably, for example, may be selected from the material which can be utilized as a light emitting material and host material mentioned later, for example.

3) A method of adjusting the emission color by adding a wavelength converting material to a layer (including a transparent substrate) on the light extraction side of the light emitting layer.
As this material, a known wavelength conversion material can be used. For example, a fluorescence conversion substance that converts light emitted from the light emitting layer into other light having a low energy wavelength can be used. The type of the fluorescence conversion substance is appropriately selected according to the wavelength of light to be emitted from the target organic EL device and the wavelength of light emitted from the light emitting layer. Further, the amount of the fluorescence conversion substance used can be appropriately selected according to the type within a range in which concentration quenching does not occur. Only one type of fluorescent conversion substance may be used, or a plurality of types may be used in combination. When a plurality of types are used in combination, white light or intermediate color light can be emitted in addition to blue light, green light, and red light.

  Examples of fluorescent light-emitting materials that can be used in the light-emitting element include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, and coumarins. Derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, Metal complexes and pyromethene derivatives of styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives Various metal complexes represented by metal complexes of the body, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of phosphorescent materials that can be used for the light-emitting element 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 light emitting element 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 Examples thereof include those having an arylsilane 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 further 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 , Etc. are preferable.
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 even 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 further 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 above-described materials, 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 500 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 even 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 further 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.

  Further, in order to alleviate the energy barrier between the cathode and the light emitting layer, the layer adjacent to the cathode may be doped with an alkali metal or an alkali metal compound. Since the organic layer is reduced by the added metal or metal compound to generate anions, the electron injecting property is increased and the applied voltage is decreased. Examples of the alkali metal compound include oxides, fluorides, and lithium chelates.

-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. In addition, the electron transport layer / electron injection layer may also function as a hole blocking layer.
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 even 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.
In addition, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer / hole injection layer may also serve this function.

(Protective layer)
In the light emitting element, the entire element may be protected by a protective layer. As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiNx and SiNxOy, metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide, Copolymerizing polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, and a monomer mixture containing tetrafluoroethylene and at least one comonomer. Copolymer, fluorine-containing copolymer having a cyclic structure in the copolymer main chain Examples thereof include a polymer, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.

  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, coating method, printing method, transfer method can be applied.

  Furthermore, the light emitting device may be sealed entirely using the barrier film and the sealing container of the present invention. Further, a moisture absorbent or an inert liquid may be enclosed 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.

(Element drive)
The light-emitting element can obtain light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can. As for the driving method of the light-emitting element, JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-214447, patents The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 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.

Gas barrier films (sample Nos. 1 to 5) in which an inorganic gas barrier layer, an organic layer, and an ultraviolet blocking layer were provided on a base film were prepared according to the following procedure. Details of the structure of each gas barrier film are as shown in Table 1.
1. Formation of Inorganic Gas Barrier Layer An inorganic gas barrier layer was formed on a 100 μm thick PET (Lumirror T60 manufactured by Toray Industries, Inc.) film using a roll-to-roll sputtering apparatus (1) shown in FIG.
As shown in FIG. 1, the sputtering apparatus (1) has a vacuum chamber (2), and a drum (3) for cooling the plastic film (6) in contact with the surface is provided at the center thereof. Has been placed. In addition, a delivery roll (4) and a take-up roll (5) for winding the plastic film (6) are disposed in the vacuum chamber (2). The plastic film (6) wound around the delivery roll (4) is wound around the drum (3) via the guide roll (7), and further the plastic film (6) is wound around the take-up roll (8) via the guide roll (8). 5) As a vacuum exhaust system, the exhaust in the vacuum chamber (2) is always performed from the exhaust port (9) by the vacuum pump (10). As a film forming system, a target (not shown) is mounted on a cathode (12) connected to a DC type discharge power source (11) to which pulse power can be applied. The discharge power source (11) is connected to the controller (13), and the controller (13) supplies the gas flow rate to the vacuum chamber (2) while adjusting the reaction gas introduction amount via the pipe (15). It is connected to the adjustment unit (14). The vacuum chamber (2) is configured to be supplied with a discharge gas having a constant flow rate (not shown).

Hereinafter, specific conditions at the time of forming the inorganic gas barrier layer will be shown.
Si was set as a target, and a pulse application type DC power source was prepared as a discharge power source (11). Moreover, a PET film having a thickness of 100 μm was prepared as a plastic film (6), and this was put on a feed roll (4) and passed to a take-up roll (5). After completing the preparation of the base material to the sputtering apparatus (1), the door of the vacuum chamber (2) was closed, the vacuum pump (10) was started, and vacuuming and cooling of the drum were started. When the ultimate pressure reached 4 × 10 ⁻⁴ Pa and the drum temperature reached 5 ° C., the plastic film (6) started to run. Argon was introduced as a discharge gas, the discharge power source (11) was turned on, plasma was generated on the Si target at a discharge power of 5 kW and a film formation pressure of 0.3 Pa, and pre-sputtering was performed for 3 minutes. Thereafter, oxygen was introduced as a reaction gas, and after the discharge was stabilized, the amounts of argon and oxygen gas were gradually reduced to lower the film forming pressure to 0.1 Pa. After confirming the stability of discharge at 0.1 Pa, a silicon oxide film was formed for a certain period of time. After the film formation was completed, the vacuum chamber (2) was returned to atmospheric pressure, and the film on which silicon oxide (inorganic gas barrier layer) was formed was taken out. The film thickness of the inorganic gas barrier layer was about 50 nm. In addition, according to each structure content in following Table 1, when forming an inorganic gas barrier layer on an organic layer, the inorganic gas barrier layer was formed by the same method.

2. Formation of organic layer 50.75 mL of tetraethylene glycol diacrylate, 14.5 mL of tripropylene glycol monoacrylate, 7.25 mL of caprolactone acrylate, 10.15 mL of acrylic acid and 10.15 mL of “EZACURE” (Sartomer) , A benzophenone mixture photopolymerization initiator) and an N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine particle (36.25 gm) as a solid substance, and 20 kHz ultrasonic wave Stir with tissue mincer for about 1 hour. The mixture, heated to about 45 ° C. and stirred to prevent settling, was pumped through a capillary with an inner diameter of 2.0 mm and a length of 61 mm into a 1.3 mm spray nozzle. Therefore, small droplets were sprayed by a 25 kHz ultrasonic sprayer and dropped on the surface of the PET film (substrate film), the inorganic gas barrier layer, or the ultraviolet ray blocking layer described later. Next, after vapor condensing on the inorganic gas barrier layer of the substrate film brought into contact with the low-temperature drum having a drum surface temperature of about 13 ° C. or the ultraviolet ray blocking layer described later, UV curing is performed by a high-pressure mercury lamp lamp (integrated irradiation amount is about 2000 mJ / cm ² ), an organic layer was formed. The film thickness was about 500 nm.

3. Formation of UV blocking layer Urethane modified polyester (Toyobo, BYRON UR-1200, solid content ratio 20%, methyl ethyl ketone, toluene, cyclohexanone mixed solution) and benzotriazole UV absorber (Ciba Geigy, Tinuvin P, solid content ratio 2% ) Was added to prepare a coating solution. According to Table 1, this coating solution was applied at a designated position of about 3 μm, dried and cured to obtain an ultraviolet blocking layer.

4). Evaluation of Physical Properties of Gas Barrier Film Various physical properties of the gas barrier film were evaluated using the following apparatus. The results are summarized in Table 1.
-Layer structure (film thickness): manufactured by Hitachi, Ltd., scanning electron microscope "S-900 type"
Water vapor transmission rate (g / m ² / day): “PERMATRAN-W3 / 31” manufactured by MOCON (conditions: 40 ° C., relative humidity 90%)
-Light transmittance of gas barrier film (%): manufactured by Shimadzu Corporation, spectrophotometer "UV3100PC"

5. Production of organic EL element The above gas barrier film is introduced into a vacuum chamber, and an IZO target (manufactured by Idemitsu Kosan Co., Ltd.) is used to form a transparent electrode made of an IZO thin film having a thickness of 0.2 μm by an inorganic gas barrier. The layer was formed on the laminated surface. An aluminum lead wire was connected from the transparent electrode (IZO) to form a laminated structure.
The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: 1.3 mass% solid content), and then vacuum-dried at 150 ° C. for 2 hours. A hole-transporting organic thin film layer having a thickness of 100 nm was formed. This was designated as substrate X.

On the other hand, on one side of a temporary support made of polyethersulfone (Sumitomo Bakelite Co., Ltd., Sumilite FS-1300) having a thickness of 188 μm,
A light-emitting organic thin film layer coating solution having the following composition was applied using a spin coater and dried at room temperature to form a light-emitting organic thin film layer having a thickness of 13 nm on the temporary support. This was designated as transfer material Y.
〔composition〕
Polyvinylcarbazole: 40 parts by mass (Mw = 63000, manufactured by Aldrich)
・ Tris (2-phenylpyridine) iridium complex: 1 part by mass (orthometalated complex) (manufactured by Chemipro Kasei Co., Ltd.)
・ Dichloroethane: 3200 parts by mass

The luminescent organic thin film layer side of the transfer material Y is superimposed on the upper surface of the hole transporting organic thin film layer of the substrate X, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, A light-emitting organic thin film layer was formed on the upper surface of the substrate X by peeling off the temporary support. This is a substrate XY.
Also, a patterned vapor deposition mask (a mask with a light emission area of 5 mm × 5 mm) is installed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm cut into 25 mm square, Al was vapor-deposited in a reduced pressure atmosphere of 0.1 mPa to form an electrode having a film thickness of 0.3 μm. Using an Al ₂ O ₃ target by DC magnetron sputtering method, an Al ₂ O ₃ was deposited in the same pattern as the Al layer and the thickness of 3 nm. An aluminum lead wire was connected from the Al electrode to form a laminated structure. A coating liquid for electron transporting organic thin film layer having the following composition is coated on the obtained laminated structure with a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron transporting organic thin film having a thickness of 15 nm is obtained. A layer was formed. This is referred to as a substrate Z.

〔composition〕
Polyvinyl butyral 2000L: 10 parts by mass (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.)
1-butanol: 3500 parts by mass Electron transporting compound having the following structure: 20 parts by mass (synthesized by the method described in JP-A No. 2001-335776)

電子輸送性化合物

Electron transport compound

  Using the substrate XY and the substrate Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and sealed with a commercially available organic EL sealing material (XNR5516 manufactured by Nagase ChemteX Corp.) did.

When a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.) was applied to the obtained organic EL element to emit light, all element samples emitted light well.
Next, the organic EL device using the gas barrier film shown in Table 1 was irradiated with a xenon lamp (approximately 300,000 lux) at 60 ° C. and 90% relative humidity for 50 hours, and then the light was emitted in the same manner to thereby reduce the relative decrease in luminance. Was measured. The results are summarized in Table 1. As shown in Table 1, the sample of the present invention having an ultraviolet transmittance of 10% or less can suppress deterioration of the element due to ultraviolet rays (Sample Nos. 1 to 4). Further, it is effective to have the ultraviolet blocking layer on the outermost surface opposite to the surface on which the gas barrier layer is formed (Sample Nos. 1 and 4). In particular, when the ultraviolet blocking layer was provided on both sides, it was further effective in suppressing element deterioration (Sample No. 4).
As can be seen from this example, it was confirmed that the sample formed according to the present invention had good transparency, gas barrier properties and ultraviolet blocking properties.

  Since the gas barrier film of the present invention has excellent transparency and barrier properties, it is suitably used as a substrate for various organic devices and a coating film for devices. Moreover, organic devices, such as a substrate for image display elements and an organic EL element of the present invention, have high durability and flexibility. For this reason, this invention has high industrial applicability.

It is explanatory drawing which shows the sputtering device used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sputtering apparatus 2 Vacuum tank 3 Drum 4 Delivery roll 5 Take-up roll 6 Plastic film 7 Guide roll 8 Guide roll 9 Exhaust port 10 Vacuum pump 11 Discharge power source 12 Cathode 13 Controller 14 Gas flow rate adjustment unit 15 Piping

Claims (13)

A transparent flexible support substrate, a layer made of an inorganic compound gas barrier layer and an organic compound consisting of is a gas barrier film formed in a plurality of layers respectively alternately above the gas barrier film containing an organic ultraviolet absorber At least one ultraviolet blocking layer is formed so as to satisfy any of the following conditions (1) to (3), and the water vapor transmission rate of the gas barrier film at 40 ° C. and 90% relative humidity is 0.005 g / m ² / day or less and the transmittance of ultraviolet light having a wavelength of 350 nm is 10% or less, and the metal constituting the inorganic compound constituting the gas barrier layer is selected from the group consisting of Si, Al, In, Sn and Zn. A gas barrier film comprising at least one selected metal.
(1) The ultraviolet blocking layer is in contact with only the layer made of the organic compound.
(2) The ultraviolet blocking layer has one surface in contact with the flexible support substrate and the other surface in contact with the layer made of the organic compound.
(3) The ultraviolet blocking layer contacts only the flexible support substrate. The inorganic compound constituting the gas barrier layer, a gas barrier film according to claim 1, characterized in that a metal oxide. The inorganic compound constituting the gas barrier layer, an oxide of Si, the gas barrier film according to claim 1 or 2, characterized in that an oxide, or oxides of Si and Al of Al. The gas barrier film according to any one of claims 1 to 3, wherein the layer made of the organic compound is a polymer layer formed by applying an ultraviolet curable monomer and curing it with ultraviolet rays. The gas barrier film according to any one of claims 1 to 4, wherein the ultraviolet blocking layer is provided on at least one outermost surface of the gas barrier film. 6. The gas barrier film according to claim 5 , wherein the ultraviolet blocking layer is provided on a support substrate surface opposite to the surface on which the gas barrier layer is formed. The gas barrier film according to claim 5 , wherein the ultraviolet blocking layer is provided on both outermost surfaces of the gas barrier film. The gas barrier film according to claim 1, wherein the condition (1) is satisfied. The gas barrier film according to claim 1, wherein the condition (2) is satisfied. The gas barrier film according to claim 1, wherein the condition (3) is satisfied. The gas barrier film according to any one of claims 1 to 4 , which has any one of the following layer structures.
D / C / A / B
C / D / A / B
C / A / B / D
D / C / A / B / D
(Here, A represents one or more units made of a layer made of an organic compound and a gas barrier layer made of an inorganic compound, B represents a layer made of an organic compound, and C represents a transparent flexible support substrate. D represents an ultraviolet blocking layer containing part or all of the organic ultraviolet absorber.) The organic device using the gas barrier film of any one of claims 1 to 11. It sealed organic device with a gas barrier film of any one of claims 1 to 11.

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