JP2008149710A - Barrier laminate manufacturing method, barrier laminate, barrier film substrate, and organic EL device. - Google Patents

Abstract

［一般式（１）において、Ｌはｍ価の連結基を表し、ｍは１〜６の整数を表す。］
【選択図】なしA method for producing a barrier laminate having high water vapor barrier properties and reduced odor is provided.
A method for producing a barrier laminate comprising a structure in which an organic layer and an inorganic layer are laminated, wherein the organic layer comprises a polymerizable composition containing a monomer represented by the following general formula (1). It forms by superposing | polymerizing under the pressure of 100 Pa or less, The manufacturing method of the barriering laminated body characterized by the above-mentioned.

[In General Formula (1), L represents an m-valent linking group, and m represents an integer of 1 to 6. ]
[Selection figure] None

Description

 The present invention relates to a method for producing a barrier laminate, a barrier laminate and a barrier film substrate obtained by the production method, and an organic electroluminescent element (organic) using the barrier laminate and / or barrier film substrate. EL element).

 Conventionally, a barrier film in which a metal oxide layer 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 has been studied to use a barrier film substrate in which a barrier laminate is formed on a plastic film. Known barrier laminates include those deposited with silicon oxide (for example, see Patent Document 1) and those deposited with aluminum oxide (for example, see Patent Document 2), both of which are water vapor permeable. Has a barrier property of about 1 g / m ² / day.

However, a substrate for use in an organic EL element or the like 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, Patent Documents 3 and 4 disclose a technique for realizing a water vapor transmission rate of less than 0.01 g / m ² / day by using a barrier laminate including an organic layer and an inorganic layer. Has been.

Although this technique is characterized in that the organic layer is formed by a polymerization reaction of acrylate or methacrylate, the odor estimated to be caused by the organic layer has been a problem. For this reason, in a barrier laminate including a laminate of an organic layer and an inorganic layer, development of a production method that has a water vapor transmission rate of less than 0.01 g / m ² / day and has no odor problem has been developed. It was desired.

Japanese Examined Patent Publication No. 53-12953 (pages 1 to 3) JP 58-217344 A (pages 1 to 4) US Pat. No. 6,413,645 US Pat. No. 6,268,695

 An object of the present invention is to provide a method for producing a barrier laminate having high water vapor barrier properties and reduced odor. The second object of the present invention is to provide a barrier laminate and a barrier film substrate obtained by the method for producing a barrier laminate, and an organic EL device using the same.

［一般式（１）において、Ｌはｍ価の連結基を表し、ｍは１〜６の整数を表す。］
（２）前記重合性組成物は、一般式（１）においてｍ＝２であるモノマーを６０〜８０質量％、一般式（１）においてｍ＝３であるモノマーおよび／または一般式（１）においてｍ＝４であるモノマーを２０〜４０質量％を含む、（１）に記載のバリア性積層体の製造方法。
（３）一般式（１）におけるＬの総炭素数が８〜１６であることを特徴とする（１）または（２）に記載のバリア性積層体の製造方法。
（４）有機層および無機層を、連続して、１００Ｐａ以下の圧力下で形成することを特徴とする（１）〜（３）のいずれか１項に記載のバリア性積層体の製造方法。
（５）前記重合性組成物を、１００Ｐａ以下の圧力下で、２Ｊ／ｃｍ²以上のエネルギーの紫外線を照射して重合させることを特徴とする、（１）〜（４）のいずれか１項に記載のバリア性積層体の製造方法。
（６）前記重合性組成物を、３０Ｐａ以下の圧力下で、０．５Ｊ／ｃｍ²以上のエネルギーの紫外線を照射して重合させることを特徴とする、（１）〜（４）のいずれか１項に記載のバリア性積層体の製造方法。
（７）（１）〜（６）のいずれか１項に記載のバリア性積層体の製造方法より製造したバリア性積層体。
（８）プラスチックフィルム基板上に、（１）〜（６）のいずれか１項に記載のバリア性積層体の製造方法より製造したバリア性積層体を有するバリア性フィルム基板。
（９）赤外線吸収法で定量した重合率の値が８８％以上であることを特徴とする、（８）に記載のバリア性フィルム基板。
（１０）（７）に記載のバリア性積層体、または、（８）若しくは（９）に記載のバリア性フィルム基板を用いた有機ＥＬ素子。
（１１）（７）に記載のバリア性積層体と、（８）または（９）に記載のバリア性フィルム基板の両方を用いた有機ＥＬ素子。 As a result of intensive studies by the inventors under the above-mentioned problems, the problem of odor in a barrier laminate having a barrier layer including an inorganic layer and an organic layer is an unreacted monomer (acrylate or methacrylate) when forming the organic layer. It was thought that it was an odor. Since the odor of the monomer is weaker with methacrylate than with acrylate, it is inherently preferable to have methacrylate as the main component. However, methacrylate is subject to polymerization inhibition by oxygen in the air. On the other hand, even if the oxygen concentration at the time of polymerization was suppressed to 0.5% or less by the nitrogen substitution method, the polymerization did not proceed sufficiently, and an odor remained on the contrary. As a result of the study by the inventors, it was found that when polymerization is performed at a pressure of 100 Pa or less, the polymerization proceeds sufficiently and the odor is reduced.
Specifically, it has been found that the above problems can be solved by the following means.
(1) A method for producing a barrier laminate comprising a structure in which an organic layer and an inorganic layer are laminated, wherein the organic layer comprises a polymerizable composition containing a monomer represented by the following general formula (1) at 100 Pa. It forms by polymerizing under the following pressures, The manufacturing method of a barriering laminated body characterized by the above-mentioned.

[In General Formula (1), L represents an m-valent linking group, and m represents an integer of 1 to 6. ]
(2) In the polymerizable composition, the monomer having m = 2 in the general formula (1) is 60 to 80% by mass, the monomer having m = 3 in the general formula (1) and / or the general formula (1). The method for producing a barrier laminate according to (1), wherein the monomer having m = 4 contains 20 to 40% by mass.
(3) The method for producing a barrier laminate according to (1) or (2), wherein the total carbon number of L in the general formula (1) is 8 to 16.
(4) The method for producing a barrier laminate according to any one of (1) to (3), wherein the organic layer and the inorganic layer are continuously formed under a pressure of 100 Pa or less.
(5) Any one of (1) to (4), wherein the polymerizable composition is polymerized by irradiation with ultraviolet rays having an energy of ² J / cm ² or more under a pressure of 100 Pa or less. A method for producing a barrier laminate as described in 1.
(6) Any of (1) to (4), wherein the polymerizable composition is polymerized by irradiating with ultraviolet rays having an energy of 0.5 J / cm ² or more under a pressure of 30 Pa or less. 2. A method for producing a barrier laminate according to item 1.
(7) A barrier laminate produced by the method for producing a barrier laminate according to any one of (1) to (6).
(8) A barrier film substrate having a barrier laminate produced by the method for producing a barrier laminate according to any one of (1) to (6) on a plastic film substrate.
(9) The barrier film substrate according to (8), wherein the polymerization rate determined by an infrared absorption method is 88% or more.
(10) An organic EL device using the barrier laminate according to (7) or the barrier film substrate according to (8) or (9).
(11) An organic EL device using both the barrier laminate described in (7) and the barrier film substrate described in (8) or (9).

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

(Method for forming barrier laminate)
The barrier laminate of the present invention is formed by laminating an organic layer and an inorganic layer. The number of layers of the organic layer and the inorganic layer is appropriately selected depending on the desired barrier ability, and may be one layer or a plurality of layers. In general, the larger the number of layers, the higher the barrier ability. Moreover, the structure in which the organic layer and the inorganic layer are laminated in the present invention includes a structure in which the organic layers are adjacent to each other or the inorganic layers are adjacent to each other. When the barrier laminate of the present invention is used for an organic EL element, in order to protect the organic EL element from moisture in the environment, it is usually at least two inorganic layers and at least one organic layer separating them. Is required. When two or more inorganic layers are present, they may be the same as or different from each other. When two or more organic layers are present, they may be the same as or different from each other.
The barrier laminate of the present invention may be formed on a device (for example, an organic EL element) or may be formed on a plastic film. What formed the barriering laminated body of this invention on the plastic film is the barriering film board | substrate of this invention.

［一般式（１）において、Ｌはｍ価の連結基を表し、ｍは１〜６の整数を表す。］ (Formation method of organic layer)
In the present invention, the organic layer is formed by polymerizing a polymerizable composition containing a monomer represented by the following general formula (1) under a pressure of 100 Pa or less, preferably under a pressure of 30 Pa or less. Here, the lower limit value of the pressure is preferably 0.01 Pa or more, and more preferably 0.1 Pa or more.

[In General Formula (1), L represents an m-valent linking group, and m represents an integer of 1 to 6. ]

  In general formula (1), m is preferably an integer of 2 to 4. The carbon number of L is preferably 3 to 24, more preferably 5 to 20, still more preferably 8 to 16, and particularly preferably 10 to 16. In the present invention, since the polymerization is carried out under a pressure of 100 Pa or less, the volatilization of the monomer becomes a problem, but the volatilization of the monomer tends to be suppressed by setting m and L within the above preferred ranges.

  When m is 2, L represents a divalent linking group. Examples of such a divalent linking group include an alkylene group (for example, 1,3-propylene group, 2,2-dimethyl-1,3). -Propylene group, 2-butyl-2-ethyl-1,3-propylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, 1,16-hexadecylene group, etc.), ether Groups, imino groups, carbonyl groups, and divalent residues in which a plurality of these divalent groups are connected in series (for example, polyethyleneoxy group, polypropyleneoxy group, propionyloxyethylene group, butyroyloxypropylene group, caproyloxy) Ethylene group, caproyloxybutylene group, etc.). Among these, an alkylene group is preferable.

  L may have a substituent, and examples of the substituent that can substitute L include an alkyl group (for example, a methyl group, an ethyl group, and a butyl group), and an aryl group (for example, a phenyl group). , Amino groups (for example, amino group, methylamino group, dimethylamino group, diethylamino group, etc.), alkoxy groups (for example, methoxy group, ethoxy group, butoxy group, 2-ethylhexyloxy group, etc.), acyl groups (for example, Acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom) And a cyano group. As the substituent, a group having no oxygen-containing functional group is preferable for the reason described later, and an alkyl group is particularly preferable. That is, when m is 2, L is most preferably an alkylene group having no oxygen-containing functional group. By adopting such a group, it becomes possible to further lower the water vapor transmission rate.

  When m is 3, L represents a trivalent linking group. As an example of such a trivalent linking group, trivalent obtained by removing one arbitrary hydrogen atom from the above-mentioned divalent linking group. Residue or trivalent residue obtained by removing one arbitrary hydrogen atom from the aforementioned divalent linking group and substituting an alkylene group, an ether group, a carbonyl group, and a divalent group in which these are connected in series Can be mentioned. Among these, a trivalent residue containing no oxygen-containing functional group obtained by removing one arbitrary hydrogen atom from an alkylene group is preferable. By adopting such a group, it becomes possible to further lower the water vapor transmission rate.

  When m is 4 or more, L represents a tetravalent or higher valent linking group. Examples of such a tetravalent linking group are obtained by removing two arbitrary hydrogen atoms from the above divalent linking group. A tetravalent residue or a tetravalent group in which any one hydrogen atom is removed from the above-described trivalent linking group and an alkylene group, an ether group, a carbonyl group, and a trivalent group in which these groups are connected in series are substituted. Residues can be mentioned. Among these, a divalent residue obtained by removing two arbitrary hydrogen atoms from an alkylene group and not containing an oxygen-containing functional group is preferable. By adopting such a group, it becomes possible to further lower the water vapor transmission rate.

Only one type of monomer represented by the general formula (1) may be used, or two or more types may be used.
The proportion of the monomer represented by the general formula (1) in the polymerizable composition is preferably 60% by mass to 100% by mass. Moreover, in this invention, the monomer of m = 2 in General formula (1) is 60-80 mass%, and the sum total of 20-40 mass of the monomer of m = 3 and / or m = 4 in General formula (1). It is preferable to use a polymerizable composition that includes 60% by mass to 80% by mass of a monomer having m = 2 in the general formula (1) and / or a monomer having m = 3 in the general formula (1). It is more preferable to use a polymerizable composition comprising 20 to 40% by mass of the monomer in formula (1) where m = 4. In particular, in the present invention, when the proportion of the monomer having m = 2 in the general formula (1) in the polymerizable composition is 60 to 80% by mass, the remaining components in the general formula (1) are m = 3 and Although various polymerizable monomers other than the monomer of m = 4 may be included, the content is preferably less than 20% by mass. Examples of various polymerizable monomers other than the monomer of m = 3 and / or m = 4 in the general formula (1) include a monomer in which m is 1 in the general formula (1), or a monomer having a structural formula later. Illustrated.

The organic layer of the present invention is preferably formed by flash vapor deposition. By forming by the flash vapor deposition method, the odor degree of the organic layer can be further reduced. However, in the above general formula (1), when a compound having m of 5 or more is employed, or when a compound having L carbon number of 24 or more is employed, the volatility is too low to make flash deposition difficult. There is.
In addition, in this invention, it is preferable to perform an organic layer and an inorganic layer continuously under the pressure of 100 Pa or less. Here, the term “continuous” means that when the inorganic layer is formed after forming the organic layer, or when the organic layer is formed after forming the inorganic layer, the pressure is always kept at 100 Pa or less. The process is performed. The lower limit of the pressure is not particularly defined, but the pressure of the organic layer is preferably ^0.01 Pa or more, and the pressure of the inorganic layer is preferably 1 × 10 ⁻⁵ Pa or more. By adopting such means, not only the cycle time of the laminated film formation can be shortened, but also the gas barrier property of the resulting barrier film substrate can be further improved.

In the present invention, the polymerizable composition can be formed by an ordinary solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, and an extrusion coating method (US Pat. No. 2). , 681,294 specification, an extrusion coating method using a hopper). Although there is no restriction | limiting in particular as a vacuum film-forming method, As mentioned above, a flash vapor deposition method is preferable.
Examples of a method for polymerizing the applied polymerizable composition include an ultraviolet polymerization method, a plasma polymerization method, an electron beam polymerization method, and a thermal polymerization method. Of these, the ultraviolet polymerization method is preferred. In this case, a photopolymerization initiator is usually added to the polymerizable composition. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959 Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Esacure series (eg, Ezacure TZM, Ezacure TZT, etc.) commercially available from Sartomer. ) And the like.

When performing ultraviolet polymerization, the pressure of the system is more preferably 30 Pa or less. The lower limit is not particularly defined, but is preferably 0.1 Pa or more. The upper limit of the pressure of the system is preferable from the viewpoint of making it difficult to inhibit polymerization by oxygen.
0.1-10 J / cm < ² > is preferable and the irradiation amount of an ultraviolet-ray is more preferable 0.2-5 J / cm < ² >. The lower limit of the irradiation amount is meant to increase the polymerization rate, and the upper limit is important because the irradiated object is not overheated. In the present invention, under a pressure of 100 Pa, or irradiated with energy 2~5J / cm ² UV polymerization are, under a pressure of 30 Pa, UV polymerization with energy irradiation of 0.5~2J / cm ² It is particularly preferable to carry out.

  The polymerization rate after polymerizing the polymerizable composition used in the present invention is preferably higher from the viewpoint of film strength. In order to further reduce the odor level, the polymerization rate is preferably 80% or more, and more preferably 88% or more. Here, the polymerization rate can be measured by a known method. For example, a method of quantifying unreacted double bonds by an infrared absorption method, a method of quantifying unreacted monomers by a high performance liquid chromatography method by an extraction method, and the like can be mentioned.

 The thickness of the organic layer in the present invention is preferably 50 nm to 5000 nm, and more preferably 200 nm to 2000 nm.

Although the preferable specific example of the methacrylate represented by General formula (1) below is shown, this invention is not limited to these.

Although the specific example of the other polymerizable monomer used for this invention below is shown, this invention is not limited to these.

(Formation method of inorganic layer)
The inorganic layer is a thin film layer 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 coating method, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable, and specifically, Japanese Patent No. 30032344, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. The forming method described in the publication can be employed.
The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but includes, for example, one or more metals selected from Mg, Si, Al, In, Sn, Zn, Ti, Ce, and Ta. Oxides, nitrides, carbides or oxynitrides, oxide carbides, nitride carbides, and the like can be used. Among these, oxides, nitrides or oxynitrides containing one or more metals selected from Mg, Si, Al, In, Sn, Zn and Ti are preferable, and particularly oxides and nitrides of Si and / or Al. Or oxynitrides are preferred. These may contain other elements as secondary components.

  The thickness of the inorganic layer is not particularly limited, but is preferably in the range of 2 nm to 500 nm, more preferably in the range of 5 nm to 300 nm, and still more preferably in the range of 20 nm to 200 nm.

(Barrier film substrate)
The barrier film substrate of the present invention is obtained by forming the barrier laminate of the present invention on a plastic film.

(Plastic film)
The plastic film used for this invention does not have a restriction | limiting in particular, According to the use application etc. of a barrier film board | substrate, it can select suitably. Specifically, polyester, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetheretherketone And thermoplastic resins such as polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic modified polycarbonate, fluorene ring-modified polyester, and acryloyl compound.

  The thickness of these plastic films is appropriately selected depending on the application, and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 500 μm. In particular, when used for an organic EL element, 20 to 300 μm is preferable. These plastic films may have an undercoat layer on one side or both sides. Examples of the undercoat layer include a matting agent layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, and a hard coat layer. The plastic film of the present invention preferably has a matting agent layer on one side of these undercoat layers.

(Layer structure)
As a layer structure of the barrier film substrate of the present invention, it has at least one organic layer and at least one inorganic layer on a plastic film. The first layer closest to the plastic film may be an organic layer or an inorganic layer. When the first layer is an organic layer, the second layer is preferably an inorganic layer, and when the first layer is an inorganic layer, the second layer is preferably an organic layer. An organic layer and an inorganic layer may be alternately stacked on the first layer and the second layer. The uppermost layer may be an organic layer or an inorganic layer. Furthermore, you may have another functional layer as an arbitrary interlayer or uppermost layer. Examples of the functional layer are the same as those of the undercoat layer.

(Organic EL device)
The barrier film substrate of the present invention can be preferably used as a substrate for an organic EL device. Although the example of the organic EL element using the barrier film substrate of this invention is shown in FIG. 1, this invention is not limited to this. In FIG. 1, 100 is a barrier film substrate of the present invention, 200 is an organic EL element constituent layer, and 300 is an organic EL element. Each constituent layer of the organic EL element is usually installed on the side of the barrier film substrate 100 of the present invention on which the barrier layer is formed. 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 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 (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

 The anode is, for example, 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 a CVD method or a plasma CVD method. It can be formed on the substrate in accordance with a method appropriately selected in consideration of suitability with the constituent material. 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, but 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. When using a plastic substrate with 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 alloy, lithium-aluminum alloy, Examples thereof include magnesium-silver alloys, rare earth metals such as indium and ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say. The cathode materials are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these publications 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 is configured from a printing method, a wet method such as 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 a CVD method or a plasma CVD method. The film can be formed according to a method appropriately selected in consideration of suitability with the material to be used. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like. Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

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

(Organic compound layer)
The organic compound layer in the present invention will be described.
The organic EL device of the present invention has at least one organic compound layer including a light emitting layer, and other organic compound layers other than the organic light emitting layer include a hole transport layer, an electron transport layer, a charge blocking layer, Examples thereof include 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. .

Organic light-emitting layer The organic light-emitting layer receives holes from the anode, hole injection layer, or hole transport layer and receives electrons from the cathode, electron injection layer, or electron transport layer when an electric field is applied. It is a layer having a function of providing a recombination 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 complexes containing transition metal atoms or lanthanoid atoms. Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum. Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

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

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

Electron Injection Layer, Electron Transport Layer The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, traquinodimethane 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 still more preferably 0.5 nm to 50 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

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

Protective layer In the present invention, the entire organic EL device 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 , Metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN x, metal nitride oxides such as SiN x O y, metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, poly Monomers containing methyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerizing the mixture, and having a cyclic structure in the copolymer main chain And a fluorine-containing copolymer, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.
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 organic EL element Furthermore, the organic EL element of this invention may seal the whole element using a sealing container.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

 As another sealing method, a so-called solid sealing method may be used. The solid sealing method is a method of providing a barrier support layer on an organic EL element. Usually, an adhesive is stacked and cured between the organic EL element and the barrier support layer. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated. Furthermore, after providing a protective layer on the barrier support layer, an adhesive may be stacked and cured. Although the barrier support may be glass, it is preferable to use 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 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 Publication No. 2784615, US Pat. Nos. 5,828,429, and 6,023,308 can be applied.

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

Example 1 Study for preparation of organic layer (1-1) Preparation of organic layer (AY-1) mainly composed of acrylate 1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd.) on a polyethylene naphthalate film ), 20 g of light acrylate 1.9ND-A), 0.6 g of UV polymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) and 200 g of 2-butanone have a liquid thickness of 5 μm. It applied using a wire bar. After drying at room temperature for 2 hours, an organic layer was formed by irradiating ultraviolet rays from a high-pressure mercury lamp in a chamber (pressure: 1 atm) in which the oxygen concentration was 0.45% by the nitrogen substitution method. At this time, the cumulative amount of UV irradiation was ² J / cm ² . The film thickness of the obtained organic layer (AY-1) was 460 nm.

(1-2) Measurement of polymerization rate About each of the organic layer after hardening produced in said (1-1), and the monomer mixture before hardening, the absorption intensity based on the carbonyl group of 1720 cm < ^-1 > vicinity in an infrared absorption spectrum, and The absorption intensity based on the carbon-carbon double bond near 810 cm ⁻¹ was measured, and the polymerization rate was calculated according to the following formula. The polymerization rate of the organic layer (AY-1) calculated by this method was 93%.
Polymerization rate (%) = {(a × d−b × c) / a × d} × 100
a: Peak intensity around 1720 cm ^{−1 of the} cured film
b: Peak intensity of the cured film near 810 cm ⁻¹
c: peak intensity around 1720 cm ^{−1 of the} monomer mixture
d: Peak intensity around 810 cm ^{−1 of the} monomer mixture

(1-3) Measurement of malodor The sensory test regarding an odor was done about the organic layer (AY-1) produced above. In the sensory test, 20 judges each smelled the film with the organic layer formed in their hands, and if it felt bad smell, it was judged positive, and if it did not feel bad smell, it was judged negative. The number of people put out was quantified as the odor level. The malodor of the organic layer (AY-1) was 19. From the above results, it was found that odor is a problem in the organic layer made of acrylate.

(1-4) Preparation of organic layer (MY-1) containing methacrylate as main component Bifunctional monomer (manufactured by Kyoeisha Chemical Co., Ltd., light ester 1.9ND, 1,9-nonanediol di) on a polyethylene naphthalate film A mixed solution of 20 g of methacrylate), 0.6 g of an ultraviolet polymerization initiator (Irgacure 907), 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, ultraviolet rays from a high-pressure mercury lamp were irradiated in a chamber (pressure: 1 atm) in which the oxygen concentration was 0.45% by the nitrogen substitution method. At this time, the cumulative irradiation amount of ultraviolet rays was 2.0 J / cm ² . However, the film was not sufficiently solidified and the desired organic layer could not be obtained. At this time, the polymerization rate was 55%. From the above results, it was found that methacrylate has a problem of polymerization reactivity.
Therefore, the coated and dried film was put in a vacuum chamber by the same method as in (1-1) above, vacuum degassed until the pressure became 3 Pa, and irradiated with ultraviolet rays from a high pressure mercury lamp. The obtained organic layer (MY-1) was obtained. When the polymerization rate was measured by the above method, the polymerization rate was 90%. At this time, the cumulative amount of UV irradiation was 1 J / cm ² . The film thickness of the produced organic layer (MY-1) was 460 nm.

(1-5) Production of Barrier Film Substrate On a polyethylene naphthalate film, a wire bar is prepared so that a mixed solution of 0.6 g of an ultraviolet polymerization initiator (Irgacure 907) and 200 g of 2-butanone has a liquid thickness of 5 μm. It applied using. Thereafter, the film dried at room temperature for 2 hours was put in a vacuum chamber and irradiated with ultraviolet rays from a high-pressure mercury lamp. Table 1 shows the pressure and the cumulative amount of UV irradiation. The malodor of the obtained organic layer was evaluated.

AY-2 and AY-3 (comparative examples) containing acrylate as a main component had a high malodor of 14 even in vacuum film formation. On the other hand, the odor degree of MY-1 was 9, and an improvement was observed. Furthermore, MY-2 with a cumulative UV dose of ² J / cm ² significantly improved the odor level to 1. In the monofunctional monomer addition system (MY-3 to MY-7), MY-3 to MY-6 to which monofunctional methacrylate was added was lower in malodor than MY-7 to which monofunctional acrylate was added. . Among MY-3 to MY-6 to which a monofunctional methacrylate was added, it was found that MY-4 to 6 having a linking group L of 10 to 16 carbon atoms in the general formula (1) has a low bad odor and is particularly preferable.
From the comparison of MY-1 and MY-8, it can be seen that MY-1 having a curing pressure of 3 Pa has a lower malodor degree than MY-8 having a curing pressure of 50 Pa.

(1-6) Preparation of various organic layers by flash vapor deposition-vacuum curing (3 Pa) A polyethylene naphthalate film (PEN film, manufactured by Teijin DuPont, trade name: Teonex Q65FA) is cut into a 20 cm square, and on its smooth surface side An organic layer was formed using an organic / inorganic laminated film forming apparatus (manufactured by Vitex Systems, Guardian 200). The organic layer deposition method of this apparatus is flash vapor deposition at an internal pressure of 3 Pa, and the irradiation energy of ultraviolet rays for polymerization is 1 J / cm ² . As a raw material for the organic layer, a mixed solution of 100 g of the monomer mixture in Table 2 and an ultraviolet polymerization initiator (ESACURE-TZT, 5 g) was used.

  In Table 2, TMPTMA represents trimethylolpropane trimethacrylate (trifunctional monomer), PETMA represents pentaerythritol tetramethacrylate (tetrafunctional monomer), and PETMA-OH represents pentaerythritol trimethacrylate (trifunctional monomer).

From the comparison between MY-1 in Table 1 and MY-21 in Table 2, it can be seen that the organic layer produced by the flash vapor deposition method has a low malodor even when the cumulative dose of ultraviolet rays is 1 J / cm ^2. . From comparison between MY-21 and MY-22 in Table 2, a bifunctional methacrylate having 9 carbon atoms in the linking group L was used rather than an organic layer using a bifunctional methacrylate having 6 carbon atoms in the linking group L. It can be seen that the organic layer has a lower malodor.
From the comparison of MY-21 (without trifunctional methacrylate), MY-23 (added 15 mass% of trifunctional methacrylate) and MY-24 to MY-25 (added 25 mass% of trifunctional methacrylate) in Table 2, trifunctional It can be seen that when the methacrylate is added, the malodor is improved, and when the added amount exceeds 20%, a level undetectable by the sensory test is reached. At this time, the polymerization rate of MY-24 was 94%. Although the polymerization rate is not changed by the addition of the trifunctional methacrylate, it can be seen that malodor is reduced.
MY-26 in Table 2 shows that even if the polyfunctional monomer to be mixed is a tetrafunctional monomer, it gives undetectable results and is preferable.

Example 2 Production of Barrier Film Substrate A polyethylene naphthalate film (PEN film, manufactured by Teijin DuPont, trade name: Teonex Q65FA) is cut into a 20 cm square, and an organic / inorganic laminated film forming apparatus (Vytex / A barrier layer was formed using System 200 (Guardian 200). In addition, since this apparatus carries out the vacuum integrated film formation of the organic layer and the inorganic layer, it is not open | released to air | atmosphere until a barrier layer is completed.

(2-1) Formation of first organic layer As raw materials for the organic layer, 75 g of 1,9-nonanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester 1.9ND), 25 g of pentaerythritol tetraacrylate, UV polymerization An organic layer was formed in the same manner as in Example 1 using a mixed solution of an initiator (ESACURE-TZT, 5 g). The film thickness was adjusted to 900 nm.

It apply | coated using the wire bar so that it might become a liquid thickness of 5 micrometers on a polyethylene naphthalate film. After drying at room temperature for 2 hours, the film was placed in a vacuum chamber, vacuum deaerated until the pressure reached 3 Pa, and irradiated with ultraviolet rays from a high-pressure mercury lamp. At this time, the integrated irradiation dose was ² J / cm ² . The film thickness of the produced organic layer was 460 nm.

(2-2) Formation of First Inorganic Layer Subsequently, using Guardian 200, an inorganic layer was formed. The inorganic layer was formed by an aluminum oxide film formed by a reactive sputtering method using a direct current pulse with aluminum as a target (reactive gas is oxygen). The film thickness of the obtained inorganic layer (aluminum oxide) was 40 nm.
(2-3) Formation of second organic layer A second organic layer was formed on the first inorganic layer in the same manner as the first organic layer.
(2-4) Formation of Second Inorganic Layer A second inorganic layer was formed on the second organic layer by the same method as that for the first inorganic layer.
(2-5) Formation of third organic layer A third organic layer was formed on the second inorganic layer in the same manner as the first organic layer.
(2-6) Formation of third inorganic layer A third inorganic layer was formed on the third organic layer in the same manner as the first inorganic layer.
As described above, the barrier film substrate BFS-1 with reduced odor according to the present invention was produced by a consistent method without taking it out of vacuum.

Measurement of water vapor transmission rate When the water vapor transmission rate at 40 ° C / 90% relative humidity was measured for BFM-1 using "PERMATRAN-W3 / 31" manufactured by MOCON, the water vapor transmission rate was below the detection limit ( 0.01 g / m ² · day or less).

Example 3 Production and Evaluation of Organic EL Element (3-1) Creation of Organic EL Element The barrier film substrate BFM-1 created in Example 2 was introduced into a vacuum chamber, and an ITO target was used on the inorganic layer side. Then, a transparent electrode made of an ITO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering. The water vapor barrier film having an ITO film was washed with 2-propanol and then subjected to UV-ozone treatment for 10 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)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
Finally, 1 nm of lithium fluoride and 100 nm of metal aluminum were sequentially deposited to form a cathode, and a 5 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL element (OEL-1).

(3-2) Installation of Gas Barrier Layer on Organic EL Element Using a thermosetting adhesive (Epotech 310, Daizonichimori Co., Ltd.), on the silicon nitride film side of the organic EL element (OEL-1), As the seal film, another barrier film substrate BFM-1 was bonded and heated at 65 ° C. for 3 hours to cure the adhesive. Thus, the sealing organic EL element (BOEL-1) was obtained.

(3-3) Evaluation of organic EL element light emitting surface condition Immediately after production, a sealed organic EL element (BOEL-1) is made to emit light by applying a voltage of 7 V using a source measure unit (Keithley, SMU2400 type). It was. When the surface of the light emitting surface was observed using a microscope, it was confirmed that all the elements gave uniform light emission without dark spots. Next, each element was allowed to stand in a dark room at 60 ° C. and 90% for 30 days, and the light emitting surface state was observed. The area of the luminescent site was 95% of the luminescent area before storage, and no dark spots were observed.

 It was recognized that the organic EL element using the barrier film substrate of the present invention was excellent in wet heat durability.

FIG. 1 is a schematic view showing a configuration of an example of an organic EL element using the barrier film substrate of the present invention.

Explanation of symbols

100 Barrier Film Substrate 200 Organic EL Element Configuration Layer 300 Organic EL Element

Claims (11)

A method for producing a barrier laminate comprising a structure in which an organic layer and an inorganic layer are laminated, wherein the organic layer comprises a polymerizable composition containing a monomer represented by the following general formula (1) at a pressure of 100 Pa or less. A method for producing a barrier laminate, wherein the barrier laminate is formed by polymerization under pressure.

[In General Formula (1), L represents an m-valent linking group, and m represents an integer of 1 to 6. ] The polymerizable composition includes 60 to 80% by mass of a monomer having m = 2 in the general formula (1), m = 3 in the general formula (1) and / or m = 4 in the general formula (1). The manufacturing method of the barriering laminated body of Claim 1 containing 20-40 mass% of monomers which are. The method for producing a barrier laminate according to claim 1 or 2, wherein the total carbon number of L in the general formula (1) is 8 to 16. The method for producing a barrier laminate according to any one of claims 1 to 3, wherein the organic layer and the inorganic layer are continuously formed under a pressure of 100 Pa or less. The barrier property according to claim 1, wherein the polymerizable composition is polymerized by irradiating with ultraviolet rays having an energy of ² J / cm ² or more under a pressure of 100 Pa or less. A manufacturing method of a layered product. 5. The polymerization composition according to claim 1, wherein the polymerizable composition is polymerized by irradiating with ultraviolet rays having an energy of 0.5 J / cm ² or more under a pressure of 30 Pa or less. 6. A method for producing a barrier laminate. The barriering laminated body manufactured from the manufacturing method of the barriering laminated body of any one of Claims 1-6. A barrier film substrate having a barrier laminate produced by the method for producing a barrier laminate according to any one of claims 1 to 6 on a plastic film substrate. 9. The barrier film substrate according to claim 8, wherein the polymerization rate determined by an infrared absorption method is 88% or more. An organic EL device using the barrier laminate according to claim 7 or the barrier film substrate according to claim 8 or 9. An organic EL device using both the barrier laminate according to claim 7 and the barrier film substrate according to claim 8 or 9.

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