JP2007253589A - Barrier film substrate and organic electroluminescence element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film substrate high in water vapor barrier properties, and is not peeled by a stress. <P>SOLUTION: The barrier film substrate comprises an organic-inorganic alternating laminate comprising at least one organic layer and at least two inorganic layers on a plastic film, and is characterized in that the organic layer contains a polymer having an oxirane ring, and the inorganic layers contain a metal oxide, a metal nitride, or a metal oxidized nitride of a metal selected from Si and Al. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a barrier film substrate, and more particularly to a laminated barrier film substrate suitable for various devices. Furthermore, this invention relates to the organic electroluminescent element (organic EL element) excellent in durability and flexibility using the said barrier film substrate.

  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 and organic electroluminescent elements (organic EL elements), plastic film substrates have begun to be used instead 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 permeability is about 1 g / m ² / day.

However, a substrate for use in an organic EL element is required to have a barrier property such that the water vapor transmission rate is less than 0.01 g / m ² / day. As a means for meeting such demands, a technique has been proposed in which a barrier film having an alternately laminated structure of organic layers / inorganic layers is produced by a vacuum deposition method (see, for example, Non-Patent Document 1).
Japanese Patent Publication No.53-12,953 (pages 1 to 3) JP 58-217,344 A (pages 1 to 4) “Thin Solid Films” (1996), Affinito et al. 290-291 (pages 63-67)

  However, the barrier film having the alternately laminated structure of the organic layer / inorganic layer has a problem in adhesion between layers, and there is a problem that the barrier film is peeled off due to deformation such as bending. When an organic EL device prepared using a barrier film substrate that is easy to peel off is stored under wet heat conditions, the original barrier property is not exhibited by peeling, and a non-luminous failure called a dark spot occurs. For this reason, development of a barrier film substrate that has high water vapor barrier properties and does not peel off due to stress has been desired.

  The first object of the present invention is to provide a barrier film substrate that has a high water vapor barrier property and does not peel off due to stress. The second object of the present invention is to provide an organic EL device using the barrier film substrate.

As a result of intensive studies, the present inventor has found that the present invention having the following configuration can solve the problems of the prior art and achieve the object of the present invention.
[1] A barrier film substrate comprising an organic-inorganic alternating laminate comprising at least one organic layer and at least two inorganic layers on a plastic film, wherein the organic layer comprises a polymer having an oxirane ring. A barrier film substrate comprising:

[2] The barrier film substrate according to [1], wherein the polymer having an oxirane ring has a structure derived from a vinyl monomer represented by the following general formula (1):

（式中、Ｒ¹¹は水素原子、アルキル基またはアリール基を表し、Ｒ¹²は水素原子、アルキル基またはハロゲン原子を表し、ａ１１、ａ１２は各々独立に１〜４の整数を表し、Ｌ¹¹、Ｌ¹²は各々独立に２価の連結基を表し、Ｌ¹³は（ａ１１＋ａ１２）価の連結基を表す。）

(Wherein R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group, R ¹² represents a hydrogen atom, an alkyl group or a halogen atom, a11 and a12 each independently represents an integer of 1 to 4, L ¹¹ , L ¹² each independently represents a divalent linking group, and L ¹³ represents an (a11 + a12) valent linking group.

[3] The barrier film substrate according to [2], wherein the polymer having an oxirane ring has a structure derived from a vinyl monomer represented by the following general formula (2):

（式中、Ｒ²¹は水素原子、アルキル基またはアリール基を表し、Ｒ²²は水素原子またはメチル基を表し、ａ２１、ａ２２は各々独立に１〜４の整数を表し、Ｌ²¹、Ｌ²²は各々独立に２価の連結基を表し、Ｌ²³は（ａ２１＋ａ２２）価の連結基を表す。）

(Wherein R ²¹ represents a hydrogen atom, an alkyl group or an aryl group, R ²² represents a hydrogen atom or a methyl group, a21 and a22 each independently represents an integer of 1 to 4, and L ²¹ and L ²² represent Each independently represents a divalent linking group, and L ²³ represents an (a21 + a22) valent linking group.

[4] The barrier film substrate according to [3], wherein R ²² in the general formula (2) is a hydrogen atom.
[5] Any one of [1] to [4], wherein at least one of the inorganic layers contains an oxide, nitride, or oxynitride of a metal selected from Si and Al. 2. The barrier film substrate according to 1.
[6] The barrier film substrate according to any one of [1] to [5], wherein a water vapor transmission rate at 40 ° C. and a relative humidity of 90% is 0.01 g / m ² · day or less. .

[7] The barrier film substrate according to any one of [1] to [6], wherein the plastic film has a glass transition temperature of 200 ° C. or higher.
[8] An organic electroluminescence device using the barrier film substrate according to any one of [1] to [7].

  The barrier film substrate of the present invention has a feature that it has a high water vapor barrier property and does not peel off due to stress. In addition, the organic EL device of the present invention does not cause non-luminous failures such as dark spots even when stored under wet heat conditions.

  First, the barrier film substrate of the present invention will be described in detail below. 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 has an inorganic-organic alternating laminate comprising at least one organic layer and at least two inorganic layers on a plastic film. The organic / inorganic alternating laminate is a laminate having an organic layer and an inorganic layer alternately from the plastic film side, and at least a first organic layer and an inorganic layer (first inorganic layer) from the plastic film side. , A laminate including a structure in which the second organic layer is laminated in this order, or a structure in which the first inorganic layer, the organic layer (first organic layer), and the second inorganic layer are laminated in this order from the plastic film side. Refers to a laminate comprising On the second organic layer (or the second inorganic layer), the second inorganic layer (or the second organic layer), the third organic layer (or the third inorganic layer), the third inorganic layer Layer (or third organic layer), fourth organic layer (or fourth inorganic layer), fourth inorganic layer (or fourth organic layer), fifth organic layer (or fifth inorganic layer) ). . . In this manner, one or more layers may be formed by alternately laminating organic layers and inorganic layers. The uppermost layer of the alternating laminate may be an inorganic layer or an organic layer.

  The barrier film substrate of the present invention may be provided with other layers as necessary in addition to the plastic film and the inorganic-organic alternating laminate. For example, another functional layer may be provided between the plastic film and the inorganic-organic alternating laminate, on the uppermost layer of the inorganic-organic alternating laminate, or on the back surface of the plastic film. The functional layer thus provided may be a single layer or a plurality of layers.

  The components of the barrier film substrate of the present invention are described in detail below.

(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, or oxynitride of Si or Al is particularly 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 each have the same composition or different compositions.

(Organic layer)
The organic layer in the barrier film substrate of the present invention contains an organic polymer having an oxirane ring (hereinafter abbreviated as the polymer of the present invention) as a main component. The polymer of the present invention can be prepared by radical polymerization of a monomer having an oxirane ring (hereinafter abbreviated as the monomer of the present invention) alone or mixed with another monomer. The polymer of the present invention preferably has a structure derived from the monomer represented by the general formula (1). In the present specification, the structure derived from a monomer refers to a partial structure incorporated into a polymer as a result of polymerizing the monomer by radical polymerization or the like.

In the general formula (1), R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group, R ¹² represents a hydrogen atom, an alkyl group or a halogen atom, a11 and a12 each independently represents an integer of 1 to 4, L ¹¹ and L ¹² each independently represent a divalent linking group, and L ¹³ represents an (a11 + a12) valent linking group.

In the general formula (1), R ¹¹ is a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, butyl group, etc.), or an aryl group (for example, phenyl group). Among these, a hydrogen atom or an alkyl group is preferable. R ¹² is a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, etc.), or a halogen atom (for example, a fluorine atom, a chlorine atom). Of these, a hydrogen atom or an alkyl group is preferred.

L ¹¹ and L ¹² each independently represent a divalent linking group, a single bond, an oxygen atom, a carbonyl group, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, etc.), A divalent group selected from an arylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, etc.), -NR'- (R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). A linking group or a divalent group formed by bonding a plurality of these divalent groups in series (for example, an alkylenearylene group, an alkyleneoxy group, an alkyleneoxyalkylene group, an alkyleneoxycarbonyl group, an aryleneoxycarbonyl group, a carboxyalkyleneoxy group) Group, a carboxyalkyleneoxycarbonyl group, etc.).
If a11 is an integer of 2 or more, R ¹¹ or L ¹¹ corresponding to each of the a11 may be different even in the same. Similarly, when a12 is an integer of 2 or more, R ¹² or L ¹² corresponding to each of the a12 may be different even in the same.

L ¹³ is a (a11 + a12) -valent linking group and is preferably a divalent to pentavalent linking group. When L ¹³ is a divalent linking group, L ¹³ has the same meaning as L ¹¹ and L ¹² . If L ¹³ is 3-5 divalent linking group, L ¹³ is the same as the linking group formed by pulling the divalent 1-3 arbitrary hydrogen atom from the linking group L ^11, L ¹² of. Valence of L ¹³ is equal to the sum of a11 and a12. For example a11 is 1, when a12 is 1, L ¹³ represents a divalent linking group. When a11 is 2 and a12 is 2, L represents a tetravalent linking group. R ¹¹ and L ¹³ may be bonded to each other to form a ring. L ¹³ may have a substituent or may be unsubstituted.

When L ¹³ has a substituent, examples of the substituent include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms such as a methyl group, An ethyl group, an iso-propyl group, a tert-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (preferably carbon). 2 to 20, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group.), An alkynyl group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. For example, propargyl group, 3-pentynyl group. And aryl groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. An amino group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 10, particularly preferably a carbon number of 0 to 6, such as an amino group, a methylamino group, a dimethylamino group, A diethylamino group, a dibenzylamino group, etc.), an alkoxy group (preferably having a carbon number of 1-20, more preferably having a carbon number of 1-12, particularly preferably having a carbon number of 1-8, such as methoxy group, ethoxy Group, a butoxy group, etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably carbon number). For example, a phenyloxy group, a 2-naphthyloxy group, etc.), an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 2 carbon atoms). 12 and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms). Yes, such as a phenyloxycarbonyl group), an acyloxy group (preferably having 2 to 20 carbon atoms, more Preferably it is C2-C16, Most preferably, it is C2-C10, for example, an acetoxy group, a benzoyloxy group, etc. are mentioned. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group), alkoxycarbonyl. An amino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably Has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group, and a sulfonylamino group (preferably 1 to 1 carbon atom). 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. Nylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group, methyl A sulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to carbon atoms). 12 and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably carbon atoms). Examples thereof include methylthio group and ethylthio group. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), a sulfonyl group (preferably C1-C20, More preferably, it is C1-C16, Most preferably, it is C1-C12, For example, a mesyl group, a tosyl group, etc. are mentioned), a sulfinyl group (preferably C1-C20, More preferably, it is C1-C16, Most preferably, it is C1-C12, for example, a methanesulfinyl group, a benzenesulfinyl group, etc.), a ureido group (preferably C1-C20, more preferably carbon) The number is 1 to 16, particularly preferably 1 to 12, and examples thereof include a ureido group, a methylureido group, and a phenylureido group. ), A phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as a diethylphosphoric acid amide group and a phenylphosphoric acid amide group. Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group Group, heterocyclic group (including hetero atoms such as nitrogen atom, oxygen atom, sulfur atom, selenium atom, etc., preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, eg imidazolyl group, pyridyl group , Furyl group, piperidyl group, morpholino group, etc.).

  The polymer of the present invention particularly preferably has a structure derived from the vinyl monomer represented by the general formula (2).

In the general formula (2), R ²¹ represents a hydrogen atom, an alkyl group or an aryl group, R ²² represents a hydrogen atom or a methyl group, a21 and a22 each independently represents an integer of 1 to 4, L ²¹ , L ²² each independently represents a divalent linking group, and L ²³ represents an (a21 + a22) valent linking group.
In the general formula (2), R ²¹ has the same meaning as R ¹¹ in the general formula (1). R ²² is a hydrogen atom or a methyl group, preferably a hydrogen atom. L ²¹ , L ²² and L ²³ have the same meanings as L ¹¹ , L ¹² and L ¹³ in the general formula (1), respectively. Valence of L ²³ is equal to the sum of a21 and a22. For example, when a21 is 1 and a22 is 1, L represents a divalent linking group. In a21 is 2, when a22 is 2, L ² represents a tetravalent linking group. R ²¹ and L ²³ may be bonded to each other to form a ring.

  Specific examples of the monomers represented by the general formulas (1) and (2) are shown below, but the monomers that can be used in the present invention are not limited to these.

  When the polymer of the present invention is a copolymer, the other monomer mixed as a raw material is also a vinyl monomer. Preferred vinyl monomers include acrylates, methacrylates, styrenes, vinyl acylates, acrylamides and the like. Of these, acrylate and methacrylate are particularly preferable.

  In this invention, it is preferable that the content rate of the monomer unit represented by General formula (1) or (2) contained in an organic layer is 10 mass%-100 mass% of an organic layer, and 20 mass%-100 It is more preferable that it is mass%, and it is especially preferable that it is 50 mass%-100 mass%.

  Examples of the method for forming the organic layer include a normal bar coating method or 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 substance during or after film formation. The method for polymerizing the organic substance 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 carrying out photopolymerization, a photopolymerization initiator is used in combination. The photopolymerization initiator is deposited simultaneously with the monomer.

Post polymerization may be performed to convert unreacted monomer to 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 due to external force and the barrier properties will be reduced. From this viewpoint, the thickness of the 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, a resin of 200 ° C. or higher is more preferable, and a resin of 250 ° C. or higher is more 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)

(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 an alkaline earth metal monoxide can be given. Examples of the alkaline earth metal contained in the alkaline earth metal monoxide include Be, Mg, Ca, Sr, and Ba. In the present invention, any alkaline earth metal 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 may 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 organic fine-particle matting agents include polymethyl methacrylate, cellulose acetate propionate, polystyrene, a treatment solution-soluble one described in US Pat. No. 4,142,894, US Pat. Polymers described in US Pat. No. 4,396,706 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 a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, or a wire bar coating method. It can be applied by a gravure coating method, a slide coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294.

(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 the 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 has an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. 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 electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element. Is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof. The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method. The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

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

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

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). 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. A dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

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

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

((Organic light emitting layer))
The organic light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer having a function of providing a field to emit light. The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. 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 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 electroluminescent element of this invention may seal the whole element 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. Before providing the alternate laminate, the organic EL element may be covered with a protective layer.

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

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

Example 1 Production and Evaluation of Barrier Film Substrate A first inorganic layer, a first organic layer, a second inorganic layer, a second organic layer, a third inorganic layer, a third layer on a plastic film Barrier film substrates (Sample BF-1 to Sample BF-5) provided with an organic layer, a fourth inorganic layer, and a fourth organic layer in this order were prepared according to the following procedure. Details of each sample 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 first film was peeled off from the band and dried until the residual solvent concentration became 0.08% by mass. After drying, both ends of the first film were trimmed, knurled, and wound up to prepare a base film PE-1 having a thickness of 100 μm. The glass transition temperature (Tg) of PE-1 was 355 ° C. (DMA method).

(2) Formation of barrier film substrate (2-1) Formation of first inorganic layer An inorganic layer (aluminum oxide) was formed on PE-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 the first organic layer On the plastic film on which the first inorganic layer is formed, 20 g of a monomer having the composition shown in Table 1 and an ultraviolet polymerization initiator (commercially available under the trade name of Ciba Irgacure 184) ) A mixed solution of 0.6 g and 2-butanone 200 g was applied using a wire bar so as to have a liquid thickness of 5 μm. After drying at room temperature for 2 hours, the film was cured by irradiation with ultraviolet rays from a high-pressure mercury lamp (accumulated irradiation amount: about ² J / cm ² ) to form a first organic layer. The film thickness was about 500 nm in all cases.

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

(2-4) Formation of second organic layer A second organic layer was formed on the second inorganic layer in the same manner as the first organic layer.

(2-5) Formation of third inorganic layer A third inorganic layer was formed on the second organic layer in the same manner as the first inorganic layer.

(2-6) Formation of third organic layer A third organic layer was formed on the third inorganic layer in the same manner as the first organic layer.

(2-7) Formation of 4th inorganic layer The 4th inorganic layer was formed on the 3rd organic layer by the method similar to the 1st inorganic layer.

  Barrier film substrates (BF-1 to 5) were prepared as described above.

(3) Physical property evaluation of barrier film substrate The physical properties of the barrier film substrate (BF-1 to 5) were evaluated by the following methods.
(3-1) Water vapor transmission rate Using a “PERMATRAN-W3 / 31” manufactured by MOCON, 20 water vapor transmission rates at 40 ° C./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.
(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.
(3-3) Evaluation Results Table 2 shows the physical property values of the barrier film substrates (BF-1 to 5) examined as described above. It can be seen that BF-2 to -5, which are barrier film substrates of the present invention, have higher yield and higher film strength than BF-1 of the comparative example. It can also be seen that the higher the monomer content of the present invention, the higher the yield and the higher the film strength.

[Example 2] Preparation and evaluation of organic EL element (1) Preparation of organic EL element The above-described barrier film substrate (BF-1 to BF-5) is introduced into a vacuum chamber, and an ITO target is used to perform DC magnetron sputtering. Thus, a transparent electrode made of an ITO thin film having a thickness of 0.2 μm was formed. 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 placed 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-5) were obtained.

(2) Evaluation of organic EL element A voltage of 9 V was applied to the organic EL elements (OEL-1 to OEL-5) to emit light. All the elements showed green light emission derived from Alq.

(3) Evaluation of wet heat storage property The organic EL device (OEL-1 to 5) was stored for 3 days under the condition of 60 ° C. and 90% relative humidity, and then light was emitted by applying a voltage of 9V. When the light emitting surface was observed with a microscope, dark spots were observed in OEL-1. On the other hand, no dark spots were observed in OEL 2 to 5.

  The barrier film substrate of the present invention has a high barrier property against water vapor and a high film strength. Further, the organic EL device having the barrier film substrate having such a feature has an advantage that no dark spot is generated. Therefore, the present invention has high industrial applicability.

Claims (8)

  A barrier film substrate comprising an organic-inorganic alternating laminate comprising at least one organic layer and at least two inorganic layers on a plastic film, wherein the organic layer comprises a polymer having an oxirane ring. A characteristic barrier film substrate. The barrier film substrate according to claim 1, wherein the polymer having the oxirane ring has a structure derived from a vinyl monomer represented by the following general formula (1).

(Wherein R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group, R ¹² represents a hydrogen atom, an alkyl group or a halogen atom, a11 and a12 each independently represents an integer of 1 to 4, L ¹¹ , L ¹² each independently represents a divalent linking group, and L ¹³ represents an (a11 + a12) valent linking group. The barrier film substrate according to claim 2, wherein the polymer having an oxirane ring has a structure derived from a vinyl monomer represented by the following general formula (2).

(Wherein R ²¹ represents a hydrogen atom, an alkyl group or an aryl group, R ²² represents a hydrogen atom or a methyl group, a21 and a22 each independently represents an integer of 1 to 4, and L ²¹ and L ²² represent Each independently represents a divalent linking group, and L ²³ represents an (a21 + a22) valent linking group. The barrier film substrate according to claim 3, wherein R ²² in the general formula (2) is a hydrogen atom.   The barrier property according to claim 1, wherein at least one of the inorganic layers contains an oxide, nitride, or oxynitride of a metal selected from Si and Al. Film substrate. The barrier film substrate according to any one of claims 1 to 5, wherein a water vapor permeability at 40 ° C and a relative humidity of 90% is 0.01 g / m ² · day or less.   The barrier film substrate according to any one of claims 1 to 6, wherein the glass transition temperature of the plastic film is 200 ° C or higher.   The organic electroluminescent element using the barrier film substrate as described in any one of Claims 1-7.