JP2007030387A - Barrier film substrate and organic electroluminescence device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film substrate having a high water vapor barrier property, capable of effectively suppressing dark spots when used as a substrate for an organic EL device, and having a high film strength.
A barrier film substrate comprising an alternating laminate of an organic layer and an inorganic layer comprising at least one organic layer and at least two inorganic layers on a plastic film, wherein the organic layer is a polyurea. 1 or more organic compounds selected from the group consisting of polyurethane, polyamide, polyimide, polyacrylate and polymethacrylate, and 99.5% by mass or more of the organic compounds contained in the organic layer are solid at 25 ° C. It is characterized by.
[Selection figure] None

Description

  The present invention relates to a barrier film substrate, and more particularly to a laminated barrier film substrate suitable for substrates of various devices, and further, organic electroluminescence excellent in durability and flexibility using the barrier film substrate. The present invention relates to an element (hereinafter referred to as “organic EL element”).

  Conventionally, a barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic film is used for wrapping articles, food, Widely used in packaging applications to prevent alteration of industrial products and pharmaceuticals

  In recent years, in the fields of liquid crystal display elements, organic EL elements, and the like, plastic film substrates have begun to be used in place of heavy and fragile glass substrates. Since the plastic film substrate can be applied to a roll-to-roll method, it is advantageous in terms of cost. However, there is a problem that the plastic film substrate is inferior in water vapor barrier property as compared with the glass substrate. For this reason, when a plastic film substrate is used for a liquid crystal display element, water vapor enters the liquid crystal cell and a display defect occurs.

In order to solve this problem, it is known to use a barrier film substrate in which a metal oxide thin film is formed on a plastic film. Known barrier film substrates include those obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) and those obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). Also has a barrier property such that the water vapor transmission rate is about 1 g / m ² / day.

However, a substrate for use in an organic EL element is required to have a high barrier property such that the water vapor transmission rate is less than 0.01 g / m ² / day. As means for meeting such demands, techniques for producing a barrier film having an alternately laminated structure of an organic layer and an inorganic layer by a vacuum deposition method have been proposed (see, for example, Patent Documents 3 to 8 and Non-Patent Document 1). .

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]) US Pat. No. 5,757,126 B1 (page 2 [2-46] to page 7 [7-7]) US Pat. No. 5,686,360B1 (2nd page [2-43] to 7th page [7-4]) US Pat. No. 6,231,939 B1 (page 1 [1-46] to page 12 [12-17]) US Pat. No. 6,492,026 B1 (page 2 [2-31] to page 8 [8-45]) US Pat. No. 6,522,067B1 (page 1 [1-56] to page 7 [7-14]) “Thin Solid Films” (1996), Affinito et al. 290-291 (pages 63-67)

However, simply increasing the water vapor barrier property of the organic EL element cannot suppress the non-light-emitting failure (hereinafter referred to as “dark spot”) occurring in the organic EL element to a satisfactory level. Moreover, although a plastic film deform | transforms with stress, such as a bending, the barrier film | membrane is damaged in such a deformation | transformation, and also the subject that barrier property falls.
In view of these problems of the prior art, the first object of the present invention is to have a high water vapor barrier property and to effectively suppress dark spots when used as a substrate of an organic EL element, and It was set to provide a film substrate with high film strength. In addition, the second object of the present invention is set to provide an organic EL element that does not generate dark spots and has excellent display characteristics.

  In order to achieve the above-mentioned object, the present inventors analyzed a conventional barrier film substrate in which an organic layer was formed by polymerization of acrylate, and intensively investigated the cause of the problem. As a result, it was found that a dark spot is generated by diffusing the residual monomer, which is a diffusible organic compound, to the organic EL element installed on the upper part of the barrier film substrate. Based on these findings, a technology having the following configurations [1] to [9] has been developed, and it has become clear that the above object can be achieved effectively.

[1] A barrier film substrate having an alternating laminate of an organic layer and an inorganic layer composed of at least one organic layer and at least two inorganic layers on a plastic film, wherein the organic layer is polyurea, It contains at least one organic compound selected from the group consisting of polyurethane, polyamide, polyimide, polyacrylate and polymethacrylate, and 99.5% by mass or more of the organic compound contained in the organic layer is solid at 25 ° C. A characteristic barrier film substrate.
[2] The barrier film according to [1], wherein the organic compound selected from the group consisting of polyurea, polyurethane, polyamide, polyimide, polyacrylate, and polymethacrylate has a carboxyl group or a phosphonic acid group. substrate.
[3] At least one of the inorganic layers includes one or more metal oxides, nitrides, or oxynitrides selected from the group consisting of Si, Al, In, Sn, Zn, and Ti. The barrier film substrate according to [1] or [2].
[4] A barrier film substrate comprising an alternating laminate of an organic layer and an inorganic layer comprising at least two organic layers and at least three inorganic layers on a plastic film, wherein the organic layer is a polyurea, It contains at least one organic compound selected from the group consisting of polyurethane, polyamide, polyimide, polyacrylate and polymethacrylate, and 99.5% by mass or more of the organic compound contained in the organic layer is solid at 25 ° C. A characteristic barrier film substrate.
[5] The barrier film according to [4], wherein the organic compound selected from the group consisting of polyurea, polyurethane, polyamide, polyimide, polyacrylate, and polymethacrylate has a carboxyl group or a phosphonic acid group. substrate.
[6] At least one of the inorganic layers includes one or more metal oxides, nitrides, or oxynitrides selected from the group consisting of Si, Al, In, Sn, Zn, and Ti. [4] The barrier film substrate according to [5].
[7] The barrier film substrate according to any one of [1] to [6], wherein a water vapor transmission rate at 40 ° C. and a relative humidity of 90% is 0.01 g / m ² · day or less. .
[8] The barrier film substrate according to any one of [1] to [7], wherein a glass transition temperature of the plastic film is 120 ° C. or higher.
[9] An organic EL device using the barrier film substrate according to any one of [1] to [8].

  The barrier film substrate of the present invention has a high water vapor barrier property, and when used as a substrate for an organic EL device, an organic compound that causes dark spots does not diffuse. Further, the film strength is high with respect to stress such as bending, and the barrier property is not easily lowered. Furthermore, the organic EL device of the present invention does not generate dark spots and has excellent display characteristics.

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

<Barrier film substrate>
The barrier film substrate of the present invention is a film substrate having at least one organic layer and at least two inorganic layers on a plastic film. As the structure of the layers, the first inorganic layer, the organic layer, and the second inorganic layer are sequentially deposited from the plastic film side. Another layer may be inserted between the plastic film and the first inorganic layer. Further, another layer may be present on the second inorganic layer.
The barrier film substrate of the present invention is preferably a film substrate having an alternating laminate of an inorganic layer and an organic layer composed of two or more inorganic layers and two or more organic layers on a plastic film. More preferably, it is a film substrate having an alternate laminate of an inorganic layer and an organic layer composed of three or more inorganic layers and two or more organic layers on a plastic film. As the structure of the layers, the first inorganic layer, the first organic layer, and the second inorganic layer are deposited in this order from the plastic film side, and the second organic layer, the third inorganic layer, Third organic layer, fourth inorganic layer. . . It may be laminated repeatedly as follows. Alternatively, the first organic layer, the first inorganic layer, the second organic layer, and the second inorganic layer are deposited in this order from the plastic film side, and the third organic layer and the third inorganic layer are further deposited thereon. , Fourth organic layer, fourth inorganic layer. . . It may be laminated repeatedly as follows. The uppermost layer of the alternating laminate may be an inorganic layer or an organic layer.
In addition, if necessary, another functional layer may be inserted between the plastic film and the alternate laminate, on the alternate laminate, or on the back surface of the plastic film. Another functional layer to be inserted may be a single layer or a multilayer.

(Inorganic layer)
The inorganic layer in this invention means the layer comprised with an inorganic material. The inorganic layer is a thin film having a dense structure capable of suppressing the permeation of gas molecules. Examples of the inorganic layer include a thin film (metal compound thin film) made of a metal compound. As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, etc. are suitable. The method can be adopted.
The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but, for example, one or more selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, or the like An oxide, nitride, oxynitride, or the like containing a metal can be used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride selected from Si, Al, Sn, and Ti in particular. Or oxynitride is preferable. These may contain other elements as secondary components.

The thickness of the inorganic layer is not particularly limited, but if the thickness is too thick, cracks due to bending stress occur, and if the thickness is too thin, the film is distributed in an island shape without forming a layer. Tend to be. Therefore, the thickness of each inorganic layer is preferably in the range of 5 nm to 500 nm, and more preferably 10 nm to 200 nm. The two or more inorganic layers may have the same composition or different compositions, and are not particularly limited.
The inorganic layer is preferably a uniform layer. Here, the “uniform layer” means a layer having a uniform composition in the layer. If it is a uniform layer, mechanically and optically discontinuous boundaries are unlikely to occur, and there is an advantage that it is suitable as a display material.

(Organic layer)
The organic layer in the barrier film substrate of the present invention contains an organic polymer as a main component. Examples of the organic polymer include polyurea, polyurethane, polyamide, polyimide, polyacrylate, and polymethacrylate. The organic polymer may be an addition polymerization polymer or a condensation polymerization polymer. The addition polymerization polymer may be a homopolymer or a copolymer. The organic polymer may be cross-linked. The organic polymer contained in the organic layer may be one type or a mixture of two or more types. The organic polymer of the present invention is formed by a polymerization reaction and / or a crosslinking reaction of monomers and / or oligomers when forming an organic layer.

  In the present invention, the organic layer is substantially free from a liquid organic compound. The liquid organic compound means an organic compound having a melting point of less than 25 ° C. and a boiling point of 25 ° C. or more. The phrase “the organic layer does not substantially contain a liquid organic compound” means that the content of the liquid organic compound contained in the organic layer is less than 0.5% by mass of the organic layer. In this invention, it is preferable that the content rate of the liquid organic compound contained in an organic layer is less than 0.1 mass% of an organic layer, and it is still more preferable that it is less than 0.01 mass%. That is, in the present invention, 99.5% by mass or more of the organic compound contained in the organic layer is solid at 25 ° C., and 99.9% by mass or more of the organic compound contained in the organic layer is solid at 25 ° C. It is particularly preferable that 99.99% by mass or more of the organic compound contained in the organic layer is solid at 25 ° C.

According to the study by the present inventors, it has been found that an organic polymer or a solid organic compound does not adversely affect the organic EL element, but a liquid organic compound adversely affects the organic EL element. Although not bound by any theory, this is because the liquid organic compound diffuses from the organic layer of the barrier film substrate to the organic EL element portion when an organic EL element is produced on the barrier film substrate. It is estimated that. The liquid organic compound contained in the organic layer is mainly an unreacted liquid monomer used when the organic layer is installed. For this reason, in this invention, when installing an organic layer, a solid monomer is used and a liquid monomer is not used substantially. In addition, the higher the melting point of the same solid monomer, the smaller the adverse effect on the organic EL element. The melting point of the solid monomer is preferably 40 ° C to 400 ° C, more preferably 60 ° C to 300 ° C.
Note that a volatile organic solvent may be used when the organic layer is installed, but the volatile organic solvent remaining in the organic layer is contrary to the spirit of the present invention. In the present invention, the organic solvent used for installing the organic layer has a boiling point of 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 100 ° C. or lower. These organic solvents are used so that the organic solvent does not substantially remain.

  In the present invention, high adhesion between the inorganic layer and the organic layer is important for maintaining the film strength. For this purpose, it is preferable to use a solid monomer having a carboxyl group or a phosphonic acid group as the solid monomer. The carboxyl group or phosphonic acid group is particularly effective when the inorganic layer is an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti. The ratio of the carboxyl group- or phosphonic acid group-containing solid monomer to the total solid monomer used for installing the organic layer is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and 2% by mass. -20% by weight is particularly preferred.

Examples of the method for forming the organic layer include a vacuum film forming method. 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, and the resistance heating vapor deposition method which is easy to control a film-forming rate is more preferable. In the present invention, an organic polymer layer is formed by polymerizing an organic compound during film formation or after film formation. The method for polymerizing the organic compound is not particularly limited, but heat polymerization, light (ultraviolet ray, visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination thereof is preferably used. When performing heat polymerization, the plastic film used as a base material needs to have appropriate heat resistance. In this case, at least the Tg (glass transition temperature) of the plastic film needs to be higher than the heating temperature. When performing photopolymerization, it is necessary to include a photopolymerization initiator in the organic layer. In the present invention, a photopolymerization initiator that is solid at room temperature is selected. The photoinitiator is deposited simultaneously with the solid monomer.
Post-polymerization may be performed to convert unreacted monomers into a polymer. Post polymerization is performed using heating, light (ultraviolet ray, visible light) irradiation, electron beam irradiation, plasma irradiation, and a combination thereof. The post polymerization may be performed immediately after the organic layer is installed or may be performed after all the layers are installed. When a plurality of organic layers are installed, post polymerization may be performed for each organic layer installation.
The film thickness of the organic layer is not particularly limited, but if it is too thin, it will be difficult to obtain film thickness uniformity, and if it is too thick, cracks will be generated by external force and the barrier properties will be reduced. From this viewpoint, the thickness of the adjacent organic layer is preferably 10 nm to 2000 nm, more preferably 20 nm to 1000 nm, and most preferably 50 nm to 500 nm.

(Plastic film)
The plastic film used for the barrier film substrate of the present invention is not particularly limited as long as it is a film that can hold each of the above layers, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, and polyurethane. And thermoplastic resins such as polyetheretherketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicycle-modified polycarbonate, fluorene ring-modified polyester, and acryloyl compound.

  Among these resins, a resin having a glass transition temperature (Tg) of 120 ° C. or higher is preferable, 200 ° C. or higher is more preferable, and 250 ° C. or higher is further preferable. Specific examples (abbreviations in parentheses: numbers indicate Tg) are polyesters, especially polyethyl naphthalate (PEN: 121 ° C.), polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.) , Fluorene ring-modified polycarbonate (BCF-PC: compound of Example 4 of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of Example 5 of JP 2000-227603 A) : 205 ° C.), fluorene ring-modified polyester (compound used in films 1 to 5 described in Example 1 of JP 2002-145998 A: 334 to 365 ° C.), acryloyl compound (JP 2002-80616 A) Example-1 of the compound: 300 ° C. or higher)

  In particular, the compound constituting the plastic film is preferably a resin having a spiro structure represented by the following general formula (1) or a resin having a cardo structure represented by the following general formula (2).

〔一般式（１）中、環αは単環式または多環式の環を表し、２つの環はそれぞれ同一若しくは異なっていてもよく、スピロ結合によって結合している。〕

[In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings may be the same or different, and are connected by a spiro bond. ]

〔一般式（２）中、環βおよび環γは単環式または多環式の環を表し、２つの環γはそれぞれ同一若しくは異なっていてもよい。また、環βおよび環γは、環β上の１つの４級炭素原子によって連結される。〕

[In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and the two rings γ may be the same or different. Ring β and ring γ are connected by one quaternary carbon atom on ring β. ]

  Since the resins represented by the general formulas (1) and (2) are compounds having high heat resistance, high elastic modulus and high tensile fracture stress, various heating operations are required in the manufacturing process and they are bent. However, it can be suitably used as a substrate material for an organic EL element or the like that is required to have a performance that is difficult to break.

  Examples of the ring α in the general formula (1) include an indane ring, a chroman ring, a 2,3-dihydrobenzofuran ring, an indoline ring, a tetrahydropyran ring, a tetrahydrofuran ring, a dioxane ring, a cyclohexane ring, and a cyclopentane ring. It is done. Examples of the ring β in the general formula (2) include a fluorene ring, an indandione ring, an indanone ring, an indene ring, an indane ring, a tetralone ring, an anthrone ring, a cyclohexane ring, and a cyclopentane ring. The ring γ in the general formula (2) includes a benzene ring, naphthalene ring, anthracene ring, fluorene ring, cyclohexane ring, cyclopentane ring, pyridine ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, and benzothiazole ring. , Indane ring, chroman ring, indole ring, α-pyrone ring and the like.

  Preferred examples of the resin having a spiro structure represented by the general formula (1) include a polymer containing a spirobiindane structure represented by the following general formula (3) in a repeating unit, and represented by the following general formula (4). And a polymer containing a spirobibenzofuran structure represented by the following general formula (5) in the repeating unit.

In general formula (3), R ³¹ and R ³² each independently represent a hydrogen atom or a substituent. R ³³ represents a substituent. R ³¹ , R ³² , and R ³³ may be linked to form a ring. m and n each independently represents an integer of 0 to 3. Preferable examples of the substituent include a halogen atom, an alkyl group, and an aryl group. R ³¹ and R ³² are more preferably each independently a hydrogen atom, a methyl group or a phenyl group. R ³³ is more preferably a chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group.

In the general formula (4), R ⁴¹ represents a hydrogen atom or a substituent. R ⁴² represents a substituent. R ⁴¹ and R ⁴² may be linked to form a ring. m and n each independently represents an integer of 0 to 3. Preferable examples of the substituent include a halogen atom, an alkyl group, and an aryl group. R ⁴¹ is more preferably a hydrogen atom, methyl group or phenyl group, and R ⁴² is more preferably a chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group.

In the general formula (5), R ⁵¹ represents a hydrogen atom or a substituent. R ⁵² represents a substituent. R ⁵¹ and R ⁵² may be linked to form a ring. m and n each independently represents an integer of 0 to 3. Preferable examples of the substituent include a halogen atom, an alkyl group, and an aryl group. R ⁵¹ is preferably a hydrogen atom, a methyl group or a phenyl group. R ⁵² is preferably a chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group.

  Further, examples of the ring β in the general formula (2) include fluorene and 1,4-bibenzocyclohexane, and examples of the ring γ include phenylene and naphthalene. Preferable examples of the resin having a cardo structure represented by the general formula (2) include a polymer containing a fluorene structure represented by the following general formula (6) in a repeating unit.

In General Formula (6), R ⁶¹ and R ⁶² each independently represent a substituent. R ⁵¹ and R ⁵² may be linked to form a ring. j and k each independently represents an integer of 0 to 4. Preferable examples of the substituent include a halogen atom, an alkyl group, and an aryl group. R ⁵¹ and R ⁵² are more preferably each independently a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a tert-butyl group or a phenyl group.

  The resin containing the structure represented by the general formulas (3) to (6) in the repeating unit may be a polymer linked by various bonding methods such as polycarbonate, polyester, polyamide, polyimide or polyurethane, A polycarbonate, polyester or polyurethane derived from a bisphenol compound having a structure represented by the general formulas (3) to (6) is preferable.

  Preferred specific examples (resin compounds (I-1) to (FL-11)) of resins having a structure represented by the general formula (1) or the general formula (2) are given below. However, the resin that can be used in the present invention is not limited thereto.

  The resin having the structure represented by the general formula (1) and the general formula (2) that can be used for the plastic film in the present invention may be used singly or in combination. Moreover, a homopolymer may be sufficient and the copolymer which combined multiple types of structure may be sufficient. When the resin is a copolymer, a known repeating unit that does not contain the structure represented by the general formula (1) or (2) in the repeating unit can be copolymerized as long as the effects of the present invention are not impaired. The resin is preferably a copolymer because it is often superior in terms of solubility and transparency than when used as a homopolymer.

  The molecular weight of the resin having the structure represented by the general formulas (1) and (2) that can be used in the present invention is preferably 10,000 to 500,000, more preferably 20,000 to 300,000 in terms of mass average molecular weight. 10,000 to 200,000 is particularly preferable. When the molecular weight of the resin is too low, film formation tends to be difficult, and mechanical properties may be deteriorated. On the other hand, if the molecular weight is too high, it is difficult to control the molecular weight in the synthesis, and the viscosity of the solution may be too high to handle. The molecular weight can be based on the corresponding viscosity.

(Hygroscopic layer)
The barrier film substrate of the present invention may have a hygroscopic layer. As a preferable example of the hygroscopic layer, a layer composed of a Group 2 metal monoxide can be given. Examples of the Group 2 metal contained in the Group 2 metal monoxide include Be, Mg, Ca, Sr, and Ba. In the present invention, any of Group 2 metals can be used, but Ca, Sr, and Ba are preferable in consideration of cost and hygroscopicity.

(Primer layer)
In the barrier film substrate of the present invention, a known primer layer can be placed on a plastic film. 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 inorganic layer by a sol-gel method. Layers can be mentioned.

(Protective layer)
The barrier film substrate of the present invention may have a protective layer. In particular, it is preferable to provide a protective layer on the back surface of the substrate. Examples of the polymer used for the protective layer include water-soluble polymers, cellulose acylates, latex polymers, water-soluble polyesters, and the like. Examples of water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, and cellulose acylates such as carboxymethyl cellulose and hydroxyethyl cellulose. Etc. Examples of the latex polymer include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylate ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer.
The protective layer can contain inorganic or organic fine particles as a matting agent to such an extent that the transparency of the barrier film substrate is not substantially impaired. Silica (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, magnesium carbonate and the like can be used as the inorganic fine particle matting agent. Examples of the organic fine-particle matting agent include polymethyl methacrylate, cellulose acetate propionate, polystyrene, a treatment solution-soluble one described in US Pat. No. 4,142,894, and US Pat. No. 4,396,706. Polymers described in the specification can be used. These fine particle matting agents preferably have an average particle size of 0.01 to 10 μm. More preferably, it is 0.05-5 micrometers. Moreover, the content is preferably 0.5 to 600 mg / m ² , more preferably 1 to 400 mg / m ² .
The protective layer is formed by a generally well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or US Pat. , 681,294 specification, it can apply by the extrusion coat method which uses the hopper.

(Antistatic layer)
The barrier film substrate of the present invention may have an antistatic layer (conductive layer). The antistatic layer is preferably formed on the back surface (the surface on which the barrier layer is not formed) of the barrier film substrate. The antistatic layer imparts a function of preventing charging during handling of the gas barrier film. Specifically, the antistatic layer is formed by providing a layer containing an ion conductive substance or conductive fine particles.
Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples include ionic polymer compounds. Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-B-49-23827, and JP-B-47-28937; Has a dissociating group in the main chain as shown in Japanese Patent Publication Nos. 50-54772, 59-14735, 57-18175, 57-18176, 57-56059, etc. Ionene type polymers: JP-B 53-13223, JP-B 57-15376, JP-B 53-45231, JP-B 55-145783, JP-B 55-65950, JP-B 55-67746, JP-B 57- See No. 11342, Japanese Patent Publication No. 57-19735, Japanese Patent Publication No. 58-56858, Japanese Patent Publication No. Sho 61-27853, and Japanese Patent Publication No. Sho 62-9346. Is such, mention may be made of cationic pendant polymers having a cationic dissociative group in the side chain.

Examples of metal oxides that are conductive fine particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _5, etc. Complex oxides are preferred, with ZnO, TiO ₂ and SnO ₂ being particularly preferred. Examples of containing different atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sb, Nb and halogen elements to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

(Other functional layers)
The barrier film substrate of the present invention may be provided with a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer and the like as required.

<Organic EL device>
Next, an organic EL element using the barrier film substrate of the present invention (hereinafter referred to as “organic EL element of the present invention”) will be described.

The organic EL device of the present invention has a cathode and an anode on a substrate, and an organic compound layer including an organic light emitting layer (hereinafter simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. 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. Each layer may be divided into a plurality of secondary layers.

(anode)
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium 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 organic EL device of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting device. 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 Group 1 metals (for example, Li, Na, K, Cs, etc.), Group 2 metals (for example, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum alloy, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, the material constituting the cathode is preferably a Group 1 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 Group 1 metal or Group 2 metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Say. The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

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

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof. Moreover, you may insert the dielectric material layer by the thickness of 0.1-5 nm between a cathode and the said organic compound layer with the fluoride, oxide, etc. of 1 group metal or 2 group metals. 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 EL device of the present invention has at least one organic compound layer including a light emitting layer, and as the organic compound layer other than the light emitting layer, as described above, a hole transport layer, an electron transport layer, a charge Examples of the layer include a block layer, a hole injection layer, and an electron injection layer.

((Formation of organic compound layer))
In the organic EL device of the present invention, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

((Light emitting layer))
The 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 which has the function to provide and to emit light. The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

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

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

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

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass. Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later. Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is 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 50 nm or less from the viewpoint of lowering the driving voltage. The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and 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.

((Hole blocking layer))
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and 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.

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

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

(Sealing)
Furthermore, the organic EL device of the present invention may be sealed using a sealing container. 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.

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

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

  The organic EL device of the present invention obtains 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. be able to. Regarding the driving method of the organic EL device of the present invention, each of JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in Japanese Patent Laid-Open No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.

  As described above, as a typical application example of the barrier film substrate of the present invention, the case where it is applied to an organic EL element has been described in detail. However, the barrier film substrate of the present invention is widely applied to uses other than the organic EL element. be able to. For example, the present invention can be applied to an image display device such as a liquid crystal display device.

  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.

Example 1 Production and Evaluation of Barrier Film Substrate Barrier film substrates BF-1 to BF-4 in which at least a first inorganic layer, a first organic layer, and a second inorganic layer are provided on a plastic film are used. It produced according to the following procedure. Details of the composition of each layer of each film substrate are as described in Table 1.

(1) Production of Plastic Film Resin A was dissolved in a dichloromethane solution so as to have a concentration of 15% by mass, and the solution was cast on a stainless steel band by a die coating method. Next, the film was peeled off from the band and dried until the residual solvent concentration became 0.08% by mass. After drying, the film was trimmed at both ends, wound up after knurling, and a plastic film serving as a substrate having a thickness of 100 μm was produced. The glass transition temperature (Tg) of the produced plastic film was 355 ° C. (DMA method).

(2) Production of barrier film substrate (2-1) Formation of first inorganic layer An inorganic layer (aluminum oxide) was formed on the plastic film produced in (1) using a sputtering apparatus. Aluminum was used as a target, argon was used as a discharge gas, and oxygen was used as a reaction gas. The film formation pressure was 0.1 Pa, and the ultimate film thickness was 50 nm.

(2-2) Formation of first organic layer On the first inorganic layer formed on the plastic film, 20 g of a monomer having the composition shown in Table 1, an ultraviolet polymerization initiator (manufactured by Ciba Specialty Chemicals, Irga) A mixture solution of 0.6 g and 200 g of 2-butanone was applied using a wire bar so as to have a liquid thickness of 5 μm. After drying at room temperature for 2 hours, it was cured by irradiating with ultraviolet rays from a high-pressure mercury lamp (accumulated dose: about ² J / cm ² ) to form an organic layer. The film thickness was about 500 nm in all cases.

(2-3) Formation of Second Inorganic Layer A second inorganic layer (aluminum oxide) was formed on the first organic layer in the same manner as the first inorganic layer.

(2-4) Formation of second organic layer As shown in Table 1, only when the barrier film substrate BF-4 is produced, the second organic layer is formed on the second inorganic layer in the same manner as the first organic layer. Two organic layers were formed.

(2-5) Formation of third inorganic layer As shown in Table 1, only when the barrier film substrate BF-4 is produced, the second inorganic layer is formed on the second organic layer in the same manner as the second inorganic layer. 3 inorganic layers (aluminum oxide) were formed.
Barrier film substrates BF-1 to BF-4 were produced as described above.

(3) Physical property evaluation of barrier film substrate The physical properties of the barrier film substrates BF-1 to BF-4 were evaluated by the following methods.
(3-1) Water vapor transmission rate Using “PERMATRAN-W3 / 31” manufactured by MOCON, 20 water vapor transmission rates at 40 ° C. and 90% relative humidity were measured for each sample. In all samples, the water vapor transmission rate was less than the detection limit (estimated to be 0.01 g / m ² · day or less) at the majority of the measurement sites.
The part which gave the finite value which water vapor permeability was observable was considered as the failure part of the barrier film substrate. The probability of finding a normal site in 20 locations was defined as the yield and expressed as a percentage. A product having a yield of 70% or more was determined to be practical.
(3-2) Film strength
The film strength of the barrier layer was examined by a method (cross-cut peeling method) based on JIS K5600-5-6 (ISO 2409). The evaluation value was expressed as a ratio (percentage) of the area where film destruction did not occur. A film having a film strength of 50% or more was determined to be practical.
(3-3) Evaluation Results Table 2 shows physical property values of the respective barrier film substrates examined as described above. The film strength is particularly good for BF-3 and BF-4 in which the organic layer contains a carboxyl group. BF-3 and BF-4 with high film strength are also good in the yield of the barrier film substrate, but BF- having an alternating laminate of an organic layer and an inorganic layer composed of two organic layers and three inorganic layers. It is clear that 4 is higher in yield.

[Example 2] Production and evaluation of organic EL element (1) Production of organic EL element Barrier film substrates BF-1 to BF-4 produced in Example 1 were introduced into a vacuum chamber, and an ITO target was used. A transparent electrode made of an ITO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering. A barrier film substrate having an ITO film was placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. 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)
NPD: film thickness 40nm
(Light emitting layer and electron transport layer)
Alq: 60 nm film thickness

Finally, 1 nm of lithium fluoride and 100 nm of metal aluminum were sequentially deposited to form a cathode.
This is put in a glove box substituted with argon gas without being exposed to the atmosphere, and sealed with a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Thus, organic EL elements OEL-1 to OEL-4 were obtained.

(2) Evaluation of organic EL element A voltage of 9 V was applied to each manufactured organic EL element to emit light. All the elements showed green light emission derived from Alq. When the light emitting surface was observed with a microscope, many dark spots were observed in OEL-1. On the other hand, no dark spots were observed in OEL2-4.

  The barrier film substrate of the present invention has a high barrier property against water vapor and a high film strength. Further, when used as an organic EL substrate, there is an advantage that no dark spot is generated. For this reason, this invention has high industrial applicability.

Claims (7)

  A barrier film substrate comprising an alternating laminate of an organic layer and an inorganic layer comprising at least one organic layer and at least two inorganic layers on a plastic film, wherein the organic layer is polyurea, polyurethane, polyamide , Containing at least one organic compound selected from the group consisting of polyimide, polyacrylate and polymethacrylate, wherein 99.5% by mass or more of the organic compound contained in the organic layer is solid at 25 ° C. Barrier film substrate.   The barrier film substrate according to claim 1, wherein the organic compound selected from the group consisting of polyurea, polyurethane, polyamide, polyimide, polyacrylate, and polymethacrylate has a carboxyl group or a phosphonic acid group.   2. The inorganic layer includes at least one oxide, nitride, or oxynitride of one or more metals selected from the group consisting of Si, Al, In, Sn, Zn, and Ti. Or the barrier film substrate according to 2;   The barrier film substrate according to any one of claims 1 to 3, wherein the alternate laminate is composed of at least two organic layers and at least three inorganic layers. The barrier film substrate according to any one of claims 1 to 4, wherein water vapor permeability at 40 ° C and relative humidity 90% is 0.01 g / m ² · day or less.   The glass transition temperature of the said plastic film is 120 degreeC or more, The barrier film substrate as described in any one of Claims 1-5 characterized by the above-mentioned. The organic electroluminescent element using the barrier film substrate as described in any one of Claims 1-6.