JP2009081122A - Method of manufacturing organic el device sealed with gas barrier film and organic el device sealed with gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To maintain gas barrier properties of an organic EL device when formed and after time has passed. <P>SOLUTION: In a method of manufacturing the organic EL device having a substrate, a pair of electrodes disposed on the substrate and an organic compound layer disposed between the electrodes, and sealed with a gas barrier film having a base material film and a gas barrier layer formed on the base material film, the gas barrier film is disposed on the electrodes to position the base material film of the gas barrier film on side faces of the electrodes. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an organic EL element sealed with a gas barrier film, an organic EL element sealed with a gas barrier film, and a method for sealing the organic EL element.

  Conventionally, a gas barrier film in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a film substrate such as a plastic substrate requires an interruption of various gases such as water vapor and oxygen It is widely used in packaging applications for preventing the deterioration of foods, industrial products and pharmaceuticals. Moreover, it is used with the board | substrate of a liquid crystal display element, a solar cell, an organic EL element other than the packaging use.

  On the other hand, Patent Document 1 discloses a laminated film in which a gas barrier layer and a protective coat layer are laminated in this order on at least one surface of a plastic film. Furthermore, it is disclosed that an electrode film is provided on the laminated film and used as a panel substrate such as a liquid crystal display panel or a touch panel.

JP 2002-174809 A

Here, when it was going to use the laminated | multilayer film of patent document 1 as a sealing film of an organic EL element, it turned out that destruction of a gas barrier layer occurs in the process of organic EL element formation. Further examination by the present inventors has revealed that this cause is that a protective coating layer is provided on the laminated film described in Patent Document 1. That is, the protective coat layer is preferably provided for protecting and strengthening the gas barrier film, but it has been found that the hard coat property of the protective coat layer destroys the gas barrier layer in the process of forming the organic EL element. .
An object of the present invention is to solve the above-mentioned problems, and aims to appropriately seal an organic EL element using a gas barrier film, and an organic material sealed with a gas barrier film. It is an object to maintain gas barrier properties at the time of formation of an EL element and thereafter.

As a result of intensive studies by the inventors based on the above problems, surprisingly, when an organic EL element is sealed by providing a gas barrier film on the electrode of the organic EL element, the gas barrier layer is surprisingly provided on the electrode side surface of the base film. It has been found that the above-mentioned problem can be solved by providing it so as to be positioned on the back surface. The present invention has been accomplished based on the above findings, and specifically has been achieved by the following means.
(1) An organic EL element having a substrate, a pair of electrodes provided on the substrate, and an organic compound layer provided between the electrodes is provided on the base film and the base film. A method for producing an organic EL device sealed with a gas barrier film having a gas barrier layer, wherein the gas barrier film is provided on an electrode so that the base film of the gas barrier film is located on a side surface of the electrode. A method for producing an organic EL device sealed with a gas barrier film.
(2) A method for producing an organic EL device sealed with the gas barrier film according to (1), further comprising providing a protective layer on the substrate and / or the gas barrier layer.
(3) The gas barrier according to (1) or (2), wherein after the gas barrier film is provided on the organic EL element, a protective layer is provided on the gas barrier layer on the side opposite to the base film. A method for producing an organic EL device sealed with a film.
(4) The gas barrier according to (1) or (2), wherein a protective layer is provided on the gas barrier layer on the side opposite to the base film before providing the gas barrier film on the organic EL element. A method for producing an organic EL device sealed with a film.
(5) The protective layer is sealed with the gas barrier film according to any one of (2) to (4), wherein the polymer film is provided by bonding the polymer film through an adhesive. A method for producing an organic EL device.
(6) The protective layer is provided by applying or vapor-depositing acrylate or methacrylate. The organic EL element sealed with the gas barrier film according to any one of (2) to (4), How to manufacture.
(7) The method of manufacturing the organic EL element sealed with the gas barrier film according to any one of (1) to (6), wherein the outermost layer on the side farther from the base film of the gas barrier layer is an organic layer. .
(8) An organic EL device sealed with a gas barrier film, produced using the method for producing an organic EL device sealed with the gas barrier film according to any one of (1) to (7).
(9) An organic EL element having a substrate, a pair of electrodes provided on the substrate, and an organic compound layer provided between the electrodes, and a base material for sealing the organic EL element A gas barrier film having a film and a gas barrier layer provided on the base film, and the gas barrier film is provided on the electrode so that the base film of the gas barrier film is located on the electrode side surface. An organic EL device sealed with a gas barrier film.
(10) The organic EL element sealed with the gas barrier film according to (9), wherein the protective layer is provided on the gas barrier layer on the side opposite to the base film.
(11) An organic EL element having a substrate, a pair of electrodes provided on the substrate, and an organic compound layer provided between the electrodes is provided on the base film and the base film. A gas barrier film having a gas barrier layer, wherein the gas barrier film is provided on an electrode such that a base film of the gas barrier film is located on a side surface of the electrode. And sealing the organic EL element.
(12) The method of sealing an organic EL element with a gas barrier film according to (11), wherein a protective layer is provided on the gas barrier layer on the side opposite to the base film.

  According to the present invention, when forming an organic EL element sealed with a gas barrier film, and thereafter, it is possible to maintain good gas barrier properties and to further reduce deterioration of the organic EL element. . In particular, even when a material having a high hard coat property is used as the protective layer of the substrate and / or the gas barrier film, the gas barrier layer is not destroyed, and thus high utility is expected.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Moreover, the organic EL element in this specification means an organic electroluminescence element.

First, an example of an embodiment of an organic EL element sealed with a gas barrier film in the present invention will be described with reference to FIG. FIG. 1 shows an example of an embodiment of an organic EL element sealed with a gas barrier film in the present invention, but the present invention is not limited to this.
In FIG. 1, 1 indicates an organic EL element, 2 indicates a gas barrier film, and 3 indicates a protective layer.
Here, the organic EL element 1 includes a substrate 11, a pair of electrodes 12 provided on the substrate, and an organic compound layer 13 provided between the electrodes. The organic EL element may include other constituent layers and constituent films as will be described later. In this configuration, the organic EL element is further sealed with the sealant 14.
A gas barrier film 2 is provided on the electrode 12 of the organic EL element 1. Here, “on the electrode” means to include both the case of being provided directly on the surface of the electrode and the case of being provided via another constituent layer or constituent film. The gas barrier film 2 includes a base film 21 and a gas barrier layer 22 provided on the base film, and is provided so that the base film 21 is located on the electrode side surface. By adopting such a configuration, it is possible to maintain good gas barrier properties even when an organic EL element sealed with a gas barrier film is formed or over time, and to further reduce deterioration of the organic EL element. It becomes possible to make it. In addition, the gas barrier film in this invention may contain the structural layer and structural film other than the base film 21 and a gas barrier film so that it may mention later. Further, the gas barrier layer may be composed of only one layer or may be composed of multiple layers, and is preferably composed of multiple layers.

In the present embodiment, the protective layer 3 is further provided on the gas barrier layer 22 on the side opposite to the base film. Here, “on the gas barrier layer” means to include both the case where it is provided directly on the surface of the gas barrier layer and the case where it is provided via another constituent layer or constituent film. Thus, by providing a protective layer, the effect that the gas barrier layer which faced the outer side of the organic EL element can be favorably maintained is obtained. In particular, there is an advantage that a hard coat layer using a highly hard coat substance can be easily used for the protective layer. Providing such a hard coat layer has the advantage that it is not easily damaged.
The protective layer may be provided after sealing the organic EL element with a gas barrier film, or may be provided before sealing. When the protective layer is provided after the organic EL element is sealed with the gas barrier film, there is an advantage that a compound having a higher hard coat property can be selected. On the other hand, when the protective layer is provided before the organic EL element is sealed with the gas barrier film, there is an advantage that the gas barrier layer of the gas barrier film can be protected during the formation of the organic EL element. The protective layer may be provided on the substrate.
Hereinafter, the organic EL element sealed with the gas barrier film in the present invention will be described in more detail.

(Gas barrier film)
The gas barrier film is a film having a function of blocking oxygen and moisture in the atmosphere. The gas barrier film in the present invention has a gas barrier layer composed of at least one organic region and an inorganic region or at least one inorganic layer, and preferably, at least one organic layer and at least one inorganic layer are laminated. Is. Organic layers and inorganic layers are usually laminated alternately. The composition constituting each layer may be a so-called gradient material layer in which an organic region and an inorganic region continuously change in the film thickness direction. Examples of the gradient materials include a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. , American Vacuum Society) ”, or a continuous layer in which the organic layer and the inorganic layer do not have an interface as disclosed in US Published Patent Application No. 2004-46497. Hereinafter, for simplification, the organic layer and the organic region are described as “organic layers”, and the inorganic layer and the inorganic region are described as inorganic layers.
The gas barrier layer has at least one inorganic layer, preferably has at least one inorganic layer and at least one organic layer, and more preferably has a structure in which inorganic layers and organic layers are alternately laminated. In the gas barrier film of the present invention, any of the lamination order of the inorganic layer and the organic layer may be formed first. From the viewpoint of adhesion to the base film, it is preferable to laminate the inorganic layer and the organic layer in this order on the base film. In particular, in the present invention, the outermost layer on the side farther from the base film of the gas barrier layer is preferably an organic layer. With such a layer structure, there is an advantage that a film having a high gas barrier property can be obtained.
Further, it is preferable that the inorganic layer or the organic layer is alternately and repeatedly laminated on the inorganic layer or the organic layer one or more times, so that the gas barrier performance can be further improved.
In the present specification, “having at least one inorganic layer and at least one organic layer alternately” includes a two-layer structure including one inorganic layer and one organic layer. included.
Although there is no restriction | limiting in particular regarding the number of layers which comprises a cas barrier film, Typically 2-30 layers are preferable, and 3-20 layers are more preferable. In addition, the barrier layer may be provided only on one side of the plastic film, or may be provided on both sides.
The gas barrier layer has at least one inorganic layer, preferably has at least one inorganic layer and at least one organic layer, and more preferably has a structure in which inorganic layers and organic layers are alternately laminated. In the gas barrier film of the present invention, any of the lamination order of the inorganic layer and the organic layer may be formed first. From the viewpoint of adhesion to the base film, it is preferable to laminate the inorganic layer and the organic layer in this order on the base film. In particular, in the present invention, the outermost layer on the side farther from the base film of the gas barrier layer is preferably an organic layer. With such a layer structure, there is an advantage that a film having a high gas barrier property can be obtained.
Further, it is preferable that the inorganic layer or the organic layer is alternately and repeatedly laminated on the inorganic layer or the organic layer one or more times, so that the gas barrier performance can be further improved.
In the present specification, “having at least one inorganic layer and at least one organic layer alternately” includes a two-layer structure including one inorganic layer and one organic layer. included.
Although there is no restriction | limiting in particular regarding the number of layers which comprises a cas barrier film, Typically 2-30 layers are preferable, and 3-20 layers are more preferable. In addition, the barrier layer may be provided only on one side of the plastic film, or may be provided on both sides.

(Base film)
The gas barrier film in the present invention usually uses a plastic film as the base film. 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.

  The gas barrier film of the present invention is preferably made of a heat-resistant material. 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 Application 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 barrier laminate of the gas barrier film faces the inside of the cell and is arranged 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 base film having a retardation value of 10 nm or less and a circularly polarizing plate (1/4 wavelength plate + (1/2 wavelength plate) + linearly polarizing plate. ) Or a linear barrier plate combined with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate.

As a base film 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 (pellet) )), 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 in the present invention is used for sealing an organic EL device, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90% or more. It is. 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.
Although there is no restriction | limiting in particular in the thickness of the plastic film used for the gas barrier film of this invention, Typically, it is 1-800 micrometers, Preferably it is 10-200 micrometers. 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.

(Inorganic layer)
The inorganic layer is not particularly limited as long as it is composed of an inorganic material and has a gas barrier property. Typically, the inorganic substance includes boron, magnesium, aluminum, silicon, titanium, zinc, tin oxide, nitride, oxynitride, carbide, hydride, and the like. These may be pure substances, or may be a mixture of multiple compositions or a gradient material layer. Of these, aluminum oxide, nitride or oxynitride, or silicon oxide, nitride or oxynitride is preferable. Although it does not specifically limit regarding the thickness of each inorganic layer which comprises a gas barrier film, Typically, it is preferable to exist in the range of 5 nm-500 nm per layer, More preferably, it is 10 nm-200 nm per layer.

As a method for forming the inorganic layer, any method can be used as long as the target thin film can be formed. For example, a sol-gel method, 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 JP-A-361774 can be employed.
In particular, when a silicon compound is formed, it is preferable to employ any one of inductively coupled plasma CVD, PVD or CVD using a microwave and a magnetic field-applied plasma set to electron cyclotron resonance conditions, Most preferably, a formation method by inductively coupled plasma CVD is employed. CVD (ECR-CVD) using microwaves set to inductively coupled plasma CVD or electron cyclotron resonance conditions and plasma applied with a magnetic field is described in, for example, Chemical Society of Japan, CVD Handbook, p. 284 (1991). It can be implemented by the method. PVD (ECR-PVD) using microwaves set to electron cyclotron resonance conditions and plasma applied with a magnetic field is, for example, Ono et al., Jpn. J. Appl. Phys. 23, No. 8, L534 ( 1984). As a raw material when using the CVD, a gas source such as silane or a liquid source such as hexamethyldisilazane can be used as a silicon supply source.

(Organic layer)
The gas barrier layer in the present invention preferably has an organic layer. In order to improve the brittleness and barrier property of the inorganic layer made of the above-mentioned inorganic substance, one or more organic layers are provided adjacent to the organic layer.

  The organic layer is formed using (1) a method using an inorganic oxide layer prepared by a sol-gel method, (2) a method in which an organic substance is laminated by coating or vapor deposition, and then cured by ultraviolet rays or an electron beam. can do. In addition, (1) and (2) may be used in combination. For example, after forming a thin film on the resin film by the method (1), an inorganic oxide layer is formed, and then (2) A thin film may be formed by a method. Hereinafter, these methods will be described in order.

(1) Sol-gel method The sol-gel method is a method in which a metal alkoxide is preferably hydrolyzed and polycondensed in a solution or in a coating film to obtain a dense thin film. At this time, an organic-inorganic hybrid material may be used in combination with a resin.

  Examples of the metal alkoxide used in the sol-gel method include alkoxysilane and / or metal alkoxide other than alkoxysilane. As the metal alkoxide other than alkoxysilane, zirconium alkoxide, titanium alkoxide, aluminum alkoxide and the like are preferable.

  The polymer used in combination during the sol-gel reaction preferably has a hydrogen bond forming group. Examples of resins having hydrogen bond-forming groups include hydroxyl group-containing polymers and derivatives thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymers, phenol resins, methylol melamine, and derivatives thereof); carboxyl groups Polymers and derivatives thereof (mono or copolymers containing units of polymerizable unsaturated acids such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, and esterified products of these polymers (vinyl esters such as vinyl acetate, Homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate)); polymers having an ether bond (polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, silicon resin, etc.); amide bond Having a polymer (> N COR) -bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent) N- of polyoxazoline or polyalkyleneimine Acylated product);> polyvinylpyrrolidone having a NC (O) -bond and derivatives thereof; polyurethane having a urethane bond; polymer having a urea bond, and the like.

  Alternatively, an organic-inorganic hybrid material can be prepared by using a monomer in combination during the sol-gel reaction and polymerizing the monomer during or after the sol-gel reaction.

During the sol-gel reaction, the metal alkoxide is hydrolyzed and polycondensed in water and an organic solvent. At this time, it is preferable to use a catalyst. As the hydrolysis catalyst, an acid (organic or inorganic acid) is generally used.
The amount of the acid used is 0.0001 to 0.05 mol per 1 mol of metal alkoxide (alkoxysilane and other metal alkoxide in the case of containing alkoxysilane and other metal alkoxide), and preferably is 0.00. 001-0.01 mol. After hydrolysis, a basic compound such as an inorganic base or an amine may be added to bring the pH of the solution to near neutrality to promote condensation polymerization.

In addition, other sol-gel catalysts such as metal chelate compounds having Al, Ti, and Zr as the central metal, organometallic compounds such as tin compounds, and metal salts such as alkali metal salts of organic acids can be used in combination.
The proportion of the sol-gel catalyst in the composition is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10%, based on the alkoxysilane that is the raw material of the sol liquid. % By mass.

  Next, the solvent used for the sol-gel reaction will be described. The solvent uniformly mixes each component in the sol liquid, adjusts the solid content of the composition, and at the same time allows it to be applied to various coating methods to improve the dispersion stability and storage stability of the composition. . These solvents are not particularly limited as long as they can fulfill the above purpose. Preferable examples of these solvents include water and organic solvents that are highly miscible with water.

For the purpose of adjusting the speed of the sol-gel reaction, an organic compound capable of multidentate coordination may be added to stabilize the metal alkoxide. Examples of organic compounds capable of multidentate coordination include β-diketones and / or β-ketoesters, and alkanolamines.
Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-tert-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.
These compounds capable of multidentate coordination can also be used for the purpose of adjusting the reaction rate when the metal chelate compound is used as a sol-gel catalyst.

  Next, a method for coating the sol-gel reaction composition will be described. The sol solution can form a thin film on the transparent film by a coating method such as curtain flow coating, dip coating, spin coating or roll coating. In this case, the hydrolysis may be performed at any time during the production process. For example, a solution of a required composition is hydrolyzed and partially condensed to prepare a desired sol solution, which is applied and dried, and a solution of the required composition is prepared and dried while hydrolyzing and partially condensing simultaneously. Method, application-After primary drying, a method of applying a water-containing liquid necessary for hydrolysis repeatedly and applying hydrolysis can be suitably employed. In addition, the coating method can take various forms. However, when productivity is important, each of the lower layer coating solution and the upper layer coating solution is required on a slide Geyser having a multistage discharge port. A method (simultaneous multi-layer method) is preferably used in which the discharge flow rate is adjusted so that the coating amount is obtained, and the formed multilayer flow is continuously placed on a support and dried.

  The drying temperature after coating is preferably 150 to 350 ° C, more preferably 150 to 250 ° C, and still more preferably 150 to 200 ° C.

In order to make the film after coating and drying more dense, irradiation with energy rays may be performed. Although there is no restriction | limiting in particular in the kind of irradiation radiation, In consideration of the influence with respect to a deformation | transformation and modification | denaturation of a support body, irradiation of an ultraviolet-ray, an electron beam, or a microwave can be used especially preferable. The irradiation intensity is ^{30mJ / cm 2 ~500mJ / cm 2} , particularly preferably ^{50mJ / cm 2 ~400mJ / cm 2} . The irradiation temperature can be employed without limitation between room temperature and the deformation temperature of the support, and is preferably 30 ° C to 150 ° C, particularly preferably 50 ° C to 130 ° C.

(2) Method of Laminating Organic Material by Application or Vapor Deposition and then Curing with Ultraviolet Ray or Electron Beam A method of forming an organic layer mainly composed of a polymer obtained by crosslinking monomers is described. The monomer used in this method is not particularly limited as long as it contains a group that can be cross-linked by ultraviolet rays or an electron beam, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxetane group. For example, epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester (meth) acrylate, etc. Among these, it is preferable that a polymer obtained by crosslinking a monomer having a bifunctional or higher functional acryloyl group or methacryloyl group as a main component. These monomers having a bifunctional or higher functional acryloyl group or methacryloyl group may be used as a mixture of two or more kinds, or as a mixture of monofunctional (meth) acrylates.
Moreover, as a monomer which has oxetane group, it is preferable to use the monomer which has a structure described in Unexamined-Japanese-Patent No. 2002-356607 General formula (3)-(6). In this case, you may mix these arbitrarily.

In the present invention, the organic layer is preferably composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group.
(Polymerizable compound)
The polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain and / or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds (acrylates and methacrylates are collectively referred to as (meth) acrylates), acrylamide compounds, styrene compounds, and anhydrous maleic compounds. An acid etc. are mentioned.

As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

Although the specific example of a (meth) acrylate type compound is shown below, this invention is not limited to these.

(Formation method of organic layer)
A method for forming the organic layer is not particularly defined, but for example, it can be formed by a 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, a gravure coating method, a slide coating method, or a method described in US Pat. No. 2,681,294. It can apply | coat by the extrusion coat method which uses a hopper. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable. In the present invention, a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in Japanese Patent Application Laid-Open Nos. 2000-323273 and 2004-25732 may be used.

  In addition, from the viewpoint of heat resistance and solvent resistance required for display applications, it is mainly composed of isocyanuric acid acrylate, epoxy acrylate, urethane acrylate having a high degree of crosslinking and a glass transition temperature of 200 ° C. or higher. Further preferred. Although it does not specifically limit about organic layer thickness, 10 nm-5000 nm are preferable, More preferably, it is 10-2000 nm, Most preferably, it is 10 nm-5000 nm. If the thickness of the organic layer is too thin, it will be difficult to obtain thickness uniformity, so that structural defects in the inorganic layer cannot be efficiently filled with the organic layer, and improvement in barrier properties may not be seen. is there. Conversely, if the organic layer is too thick, the organic layer is likely to crack due to an external force such as bending, which may cause a problem that the barrier property is lowered.

(Protective layer)
The protective layer used in the present invention can be selected from a wide range as long as it does not depart from the gist of the present invention. For example, in the present invention, particularly, a polymer film attached with an adhesive, and acrylate or methacrylate Those provided by coating or vapor deposition are preferred.
Here, as a polymer film, the same resin film as a base film used for a gas barrier film, and a well-known protective film are mentioned. Moreover, as an adhesive agent, a well-known thing can be employ | adopted and a thermoplastic adhesive agent is preferable. Thus, there exists an advantage that a protective layer can be provided simply by sticking a polymer film with an adhesive agent.
On the other hand, examples of the application method when applying or vapor-depositing acrylate or methacrylate include methods such as spray coating and bar coating, and examples of the vapor deposition method include flash vapor deposition. Thus, there exists an advantage that a thinner protective layer can be provided by apply | coating or vapor-depositing an acrylate or a methacrylate.
Furthermore, the protective layer of the present invention may contain inorganic fine particles as additives.

  The gas barrier film in the present invention may be provided with various functional layers in addition to the inorganic layer, the organic layer, and the protective layer.

In the gas barrier film of the present invention, 23 ° C., an oxygen permeability at 90% relative humidity is suitably to be ^{0~0.02ml / m 2 · day · atm} , 0~0.01ml / m 2 · day · It is preferably atm, more preferably 0 to 0.005 ml / m ² · day · atm. It is preferable that the oxygen permeability at 23 ° C. and relative humidity 90% is 0.02 ml / m ² · day · atm or less because deterioration of the organic EL element due to oxygen can be substantially eliminated.

In addition, the gas barrier film in the present invention suitably has a water vapor transmission rate of 0 to 0.02 g / m ² · day at 23 ° C. and 100% relative humidity, and 0 to 0.01 g / m ² · day. It is preferable that it is 0 to 0.005 g / m ² · day.

<Organic EL device>
As an organic EL element, an organic compound layer having a pair of electrodes (a cathode and an anode) on a substrate and including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between the electrodes. Have 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. 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 a single 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, each element which comprises an organic EL element is demonstrated in detail.

(substrate)
The board | substrate used for the well-known organic EL element can employ | adopt widely as a board | substrate used for the organic EL element in this invention. The substrate may be a resin film or a gas barrier film. The gas barrier films described in JP-A No. 2004-136466, JP-A No. 2004-148666, JP-A No. 2005-246716, JP-A No. 2005-262529, and the like can also be preferably used.

  Although the thickness of the board | substrate used by this invention is not prescribed | regulated in particular, 30 micrometers-700 micrometers are preferable, More preferably, they are 40 micrometers-200 micrometers, More preferably, they are 50 micrometers-150 micrometers. Further, in any case, the haze is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 90%. That's it.

(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. The transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Electrode Film” published by CMC (1999). When using a plastic substrate with low heat resistance as the substrate, ITO or IZO is used, and a transparent anode formed 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 Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as 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, a material mainly composed of aluminum is preferable.
The material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The cathode material is described in detail in JP-A-2-15595 and JP-A-5-121172. 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 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.

(Light emitting layer)
The organic EL 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.

-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, and receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines the holes and electrons. It is a layer having a function of providing light and emitting light. The light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the 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 kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, 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 the fluorescent light-emitting material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyralidine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Typical examples include ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives. Various metal complexes are, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.
Although it does not specifically limit as said 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 the lanthanoid atom 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.

  Examples of the host material contained in the light emitting layer 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 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.

-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.

-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.

-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.
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.

  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 is not limited to the specific examples shown below.

Example 1 Production and Evaluation of Gas Barrier Film A gas barrier film (Sample Nos. 101 to 104) in which an inorganic layer and an organic layer were provided on a base film was produced according to the following procedure. Details of the structure of each gas barrier film are as shown in Table 1. A PEN (manufactured by Teijin DuPont Co., Ltd., Q65A) film having a thickness of 100 μm was used as the base film.

[1] Formation of inorganic layer (X) An inorganic layer of aluminum oxide was formed using a reactive sputtering apparatus. Specific film forming conditions are shown below.
The vacuum chamber of the reactive sputtering apparatus was depressurized to an ultimate pressure of 5 × 10 ⁻⁴ Pa with an oil rotary pump and a turbo molecular pump. Next, argon was introduced as a plasma gas, and power of 2000 W was applied from a plasma power source. A high-purity oxygen gas was introduced into the chamber, the film formation pressure was adjusted to 0.3 Pa, and the film was formed for a certain period of time to form an aluminum oxide inorganic layer. The obtained aluminum oxide film had a thickness of 40 nm and a film density of 3.01 g / cm ³ .

[2] Formation of Organic Layer (Y, Z) The organic layer is divided into a film formation method (organic layer Y) by solvent coating under normal pressure and a film formation method (organic layer Z) by flash vapor deposition under reduced pressure. Done using the street. Specific film formation contents are shown below.
[2-1] Film formation by solvent application under normal pressure (organic layer Y)
As a photopolymerizable acrylate, 9 g of tripropylene glycol diacrylate (TPGDA: manufactured by Daicel Cytec) and 0.1 g of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907) were dissolved in 190 g of methyl ethyl ketone, did. This coating solution is applied to a base film using a wire bar, and an irradiance is applied using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under a nitrogen purge with an oxygen concentration of 0.1% or less. The organic layer Y was formed by irradiating ultraviolet rays at 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² . The film thickness was about 500 nm.

[2-2] Film formation by flash evaporation under reduced pressure (organic layer Z)
As a photopolymerizable acrylate, 9.7 g of butylethylpropanediol diacrylate (BEPGA: manufactured by Kyoeisha Chemical Co., Ltd.) and a photopolymerization initiator (manufactured by Lamberti spa, 0.3 g of EZACURE-TZT) were mixed to obtain a vapor deposition solution. This vapor deposition solution was vapor-deposited on the substrate by a flash vapor deposition method under the condition that the internal pressure of the vacuum chamber was 3 Pa. Then the conditions of the same degree of vacuum, thereby forming an organic layer Z and an irradiation dose of 2J / cm ^2. The film thickness was about 1200 nm. The organic layer Z was formed using an organic / inorganic laminated film forming apparatus Guardian 200 (manufactured by Vytex Systems).

[3] Production of gas barrier film The gas barrier film was produced by sequentially forming the inorganic layer and the organic layer on the base film according to the constitution of each sample described in Table 1. The production method was performed in the following three ways.
[3-1] Method of repeating organic layer formation by solvent coating and inorganic layer formation under reduced pressure (Lamination A)
Organic layers and inorganic layers were alternately laminated on the base film. When laminating an inorganic layer on top of an organic layer, the organic layer is formed by solvent application, and then placed in a vacuum chamber and depressurized, and after maintaining for a certain time in a state where the degree of vacuum is 10 ⁻³ Pa or less, the inorganic layer Was deposited. When the organic layer was laminated on the inorganic layer, the organic layer was formed by solvent coating immediately after the inorganic layer was formed.
[3-2] Method for consistently forming an organic layer and an inorganic layer under reduced pressure (Lamination B)
The organic layer and the inorganic layer were laminated | stacked using the above-mentioned organic inorganic laminated film-forming apparatus Guardian200. In this apparatus, both the organic layer and the inorganic layer are formed in a reduced pressure environment, and the organic and inorganic layer forming chambers are connected. Therefore, it is possible to continuously form the film in a reduced pressure environment. Therefore, it is not released to the atmosphere until the gas barrier layer is completed.
[3-3] Method of forming an organic layer by solvent coating only on the first layer, and forming the remaining layer in a consistent manner under reduced pressure (Lamination C)
A first organic layer was formed on the substrate by a solvent coating method. Subsequently, the base film having the first organic layer was put in a vacuum chamber and the pressure was reduced, and the inorganic film and the organic layer were alternately formed after maintaining the degree of vacuum at 10 ⁻³ Pa or less for a certain time.

[4] Film Formation of Protective Layer (P1) In the gas barrier film prepared above, a protective layer was formed on the outermost surface of the gas barrier layer as necessary. The film formation contents of the protective layer are specifically shown below.
As a photopolymerizable acrylate, 9 g of dipentaerythritol hexaacrylate (DPHA: manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.1 g of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907) are dissolved in 190 g of methyl ethyl ketone and applied as a coating solution. It was. This coating solution is applied to a flexible support substrate using a wire bar, and a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge with an oxygen concentration of 0.1% or less. The protective layer P1 was formed by irradiating ultraviolet rays having an illuminance of 350 mW / cm ² and an irradiation amount of 1000 mJ / cm ² . The film thickness was about 1000 nm.

[5] Physical property evaluation of gas barrier film Various physical properties of the gas barrier film were evaluated using the following apparatus.
[Layer structure (film thickness)]
The ultra-thin section of the film sample was observed and measured with a scanning electron microscope “S-900 type” manufactured by Hitachi, Ltd.

[Water vapor transmission rate (g / m ² / day)]
It was measured using “PERMATRAN-W3 / 31” (condition: 40 ° C., relative humidity 90%) manufactured by MOCON. Moreover, the value below 0.01 g / m < ² > / day which is the measurement limit of the said MOCON apparatus was supplemented using the following method. First, metal Ca was vapor-deposited directly on the gas barrier film, and the measurement sample was prepared by sealing the film and the glass substrate with a commercially available organic EL sealing material so that the vapor-deposited Ca was inside. Next, the measurement sample was kept under the above temperature and humidity conditions, and the water vapor transmission rate was determined from the change in optical density of the metal Ca on the gas barrier film (the metal gloss decreased due to hydroxylation or oxidation).

[Measurement of X-ray reflectivity (film density of inorganic layer)]
Measurement was performed using an ATX-G manufactured by Rigaku Corporation using an evaluation sample in which an inorganic layer was formed on a Si wafer. The film density of the inorganic layer thin film was calculated from the measurement results.

[Example 2] Production and evaluation of organic EL element [1] Production of substrate of organic EL element A conductive glass substrate having an ITO film (surface resistance value 10Ω / □) was washed with 2-propanol for 10 minutes. UV-ozone treatment was performed. The following organic compound 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 40 nm
(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] Cleaning and drying of gas barrier film The gas barrier film (sample Nos. 101 to 104) produced in Example 1 was subjected to the following cleaning process or cleaning process and drying process before being bonded to the organic EL element. did.
First, the gas barrier film was bonded to and peeled from a weak pressure-sensitive adhesive sheet (EC-310: manufactured by Sumilon Co., Ltd., adhesive strength 0.8 N / 20 mm vs glass plate) to remove foreign matter on the surface. Next, oxygen gas is introduced into the vacuum chamber containing the gas barrier film, the degree of vacuum is adjusted to about 6 Pa, and the plasma treatment is performed for 2 minutes with an RF plasma apparatus (RFX-500: manufactured by Advanced Energy) with an RF power of 20 W. The organic substances adhering to the surface of the gas barrier film were removed. Subsequently, the gas barrier film was heated and dried at 80 ° C. for 1 hour or more while maintaining the condition of 10 ⁻² Pa or less.

[3] Installation of gas barrier film on organic EL element Using a thermosetting adhesive (Epotec 310, Daizonitomoly Co., Ltd.), the surface of the gas barrier film on the side having the gas barrier layer or the opposite side of the gas barrier layer The surface and the organic EL element were bonded together and heated at 65 ° C. for 3 hours to cure the adhesive. 20 organic EL elements (Sample Nos. 201 to 214) sealed in this way were produced.

[4] Installation of protective member (protective film or protective layer) If necessary, the protective film (H) or protective layer (P2) on the surface of the gas barrier film bonded to the organic EL element (the surface not bonded to the organic EL element) ) Were installed sequentially. Specific contents are shown below.
[4-1] Bonding of Protective Film (H) A 25 μm thick PET (Toray, Lumirror T-60) film or a protective layer (P1) is previously applied to the surface of the gas barrier film via an adhesive layer. The applied film was bonded.
[4-2] Formation of Protective Layer (P2) The protective layer (P1) described above was formed on the surface of the gas barrier film to form a protective layer (P2).

[5] Evaluation of organic EL element light emitting surface condition An organic EL element (sample Nos. 201 to 214) immediately after preparation was made to emit light by applying a voltage of 7 V using a source measure unit (SMU2400 type, 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.
Next, each element was allowed to stand in a dark room at 60 ° C. and 90% relative humidity for 24 hours, and then the light emitting surface state was observed. The ratio of elements in which dark spots larger than 300 μm in diameter were observed was defined as a failure rate, and the failure rates of the respective elements are shown in Table 2. Table 2 also shows the evaluation of adhesion between the organic EL element and the gas barrier film.
Sample No. was changed except that the base film was changed from a PEN film to a biaxially stretched polyethylene terephthalate (PET) film (thickness: 100 μm) marketed by Toray Industries under the trade name Lumirror T60. When barrier films provided in the same manner as in 101 were prepared, barrier films having equivalent performance could be obtained regardless of the base film.
Similarly, using the barrier film obtained by changing the base film, sample No. When an organic EL element similar to that of 202 was prepared, an element having the same performance could be obtained regardless of the base film.

An example of the schematic diagram of the organic EL element sealed with the gas barrier film in this invention is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic EL element 11 Board | substrate 12 Electrode 13 Organic compound layer 14 Sealant 2 Gas barrier film 21 Base film 22 Gas barrier layer 3 Protective layer

Claims (12)

An organic EL element having a substrate, a pair of electrodes provided on the substrate, and an organic compound layer provided between the electrodes is a base film, and a gas barrier layer provided on the base film A method for producing an organic EL device sealed with a gas barrier film comprising: the gas barrier film is provided on an electrode such that a base film of the gas barrier film is positioned on a side surface of the electrode. A method for producing an organic EL device sealed with a gas barrier film. Furthermore, the method of manufacturing the organic EL element sealed with the gas barrier film of Claim 1 including providing a protective layer on a board | substrate and / or a gas barrier layer. The organic EL element is sealed with the gas barrier film according to claim 1, wherein a protective layer is provided on the gas barrier layer on the side opposite to the base film after providing the gas barrier film. A method for manufacturing an organic EL element. Before providing a gas barrier film in an organic EL element, it is sealed with the gas barrier film according to claim 1 or 2, wherein a protective layer is provided on the gas barrier layer opposite to the base film. A method for manufacturing an organic EL element. 5. The organic EL device sealed with a gas barrier film according to claim 2, wherein the protective layer is provided by bonding a polymer film through an adhesive. how to. The method for producing an organic EL element sealed with a gas barrier film according to any one of claims 2 to 4, wherein the protective layer is provided by applying or vapor-depositing acrylate or methacrylate. The method of manufacturing the organic EL element sealed with the gas barrier film of any one of Claims 1-6 whose outermost layer on the side far from the base film of a gas barrier layer is an organic layer. The organic EL element sealed with the gas barrier film manufactured using the method of manufacturing the organic EL element sealed with the gas barrier film of any one of Claims 1-7. An organic EL element having a substrate, a pair of electrodes provided on the substrate, an organic compound layer provided between the electrodes, and a base film for sealing the organic EL element; A gas barrier film having a gas barrier layer provided on the base film, and the gas barrier film is provided on the electrode so that the base film of the gas barrier film is located on the side surface of the electrode. An organic EL element sealed with a gas barrier film. The organic EL element sealed with the gas barrier film according to claim 9, wherein a protective layer is provided on the gas barrier layer on the side opposite to the base film. An organic EL device having a substrate, a pair of electrodes provided on the substrate, and an organic compound layer provided between the electrodes, a base film, and a gas barrier layer provided on the base film The gas barrier film is provided on the electrode so that the base film of the gas barrier film is located on the side surface of the electrode. A method for sealing an element. The method of sealing an organic EL element with a gas barrier film according to claim 11, wherein a protective layer is provided on the gas barrier layer on the side opposite to the base film.

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