JP2012076403A - Barrier film, and organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a uniform film capable of achieving both of barrier performance and bending resistance so as to be applied to an element or the like requiring barrier property such as a substrate for an organic electronic device.SOLUTION: A barrier film has at least one layer of organic layer on a resin substrate, wherein a first SiO(x>2) layer having a thickness of 5 to 150 nm on the organic layer and at least two layers of inorganic layers which contain silicon atoms and oxygen atoms are formed on the SiO(x>2) layer.

Description

  The present invention relates to a barrier film and an organic electronic device using the same. More specifically, the present invention relates to a barrier film having excellent water vapor barrier performance and an organic electronic device using the barrier film.

  Conventionally, a gas 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 substrate or film is used for packaging of goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent alteration of products such as industrial products and pharmaceuticals.

  In addition to packaging applications, they are used in liquid crystal display elements, photoelectric conversion elements (solar cells), organic electroluminescence (organic EL) substrates, and the like.

  Aluminum foil or the like is widely used as a packaging material in the field of such a liquid crystal display element or the like, but disposal after use is a problem. In addition, it is basically opaque and has a problem that the contents cannot be confirmed from the outside. Furthermore, since transparency is required in the field of solar cell materials, aluminum foil or the like cannot be applied.

  In particular, transparent substrates, which are being applied to liquid crystal display elements, organic EL elements, photoelectric conversion elements, etc., can be produced on a roll-to-roll basis in addition to the recent demands for weight reduction and size increase. In addition, there are high demands such as long-term reliability, high degree of freedom in shape, and the ability to display curved surfaces. For this reason, film substrates such as transparent plastics have begun to be used instead of glass substrates that are heavy, easily broken, and difficult to increase in area.

  However, a film substrate such as a transparent plastic has a problem that the barrier property is inferior to glass. For example, when a film base plate is used as a material for an organic electronic device, if a substrate with poor barrier properties is used, water vapor or air permeates and the organic film deteriorates, which may impair photoelectric conversion efficiency or durability. Become.

  In addition, when a polymer substrate is used as a substrate for an electronic device, oxygen and water molecules permeate the polymer substrate and penetrate and diffuse into the electronic device, thereby degrading the device. Cause the problem that the degree of vacuum required in can not be maintained.

In order to solve such problems, it is known to deposit a metal oxide thin film on a film substrate to form a gas barrier film substrate. Recently, as a barrier film made of an organic substance that is weak against moisture, such as an organic EL element, barrier performance is required such that the water vapor transmission rate is less than 1 × 10 ⁻³ g / m ² · day.

  On the other hand, as a method capable of forming a film by a simple coating process rather than a vapor deposition method that requires a vacuum process, the film was converted by applying a conversion treatment to a film coated with a silicon compound coating solution such as polysilazane on the substrate. Several methods for forming a gas barrier layer made of a silica film are also known (for example, Patent Document 1). Patent Document 1 discloses a process of converting a polysilazane coating film into a silica film by oxygen plasma discharge treatment under atmospheric pressure, and a gas barrier layer can be formed without requiring a vacuum process.

It is known that film formation by these coating methods can form a film with extremely high surface smoothness, and it is possible to avoid deterioration of smoothness due to particles, which is a fundamental problem of the vacuum atomic deposition method. However, the water vapor transmission rate of the obtained film is 0.35 g / (m ² · 24 h), which cannot be said to be a gas barrier layer applicable to the device as described above.

  Further, in the method described in Patent Document 1, although a single film of silicon dioxide is formed, it is necessary to increase the film thickness of the gas barrier layer in order to realize the gas barrier property that has been required recently. When the barrier film is formed by the modification treatment of the coating film, it is accompanied by a very large film shrinkage. Therefore, if the coating film thickness is too thick, cracks are generated during the modification to the barrier film. Therefore, a desired gas barrier property is achieved by laminating a plurality of thin films that do not cause cracks. However, simply laminating a plurality of layers is insufficient to realize the above-described level of gas barrier properties.

  Patent Document 2 discloses a gas barrier film in which a silicon oxynitride layer, a silicon nitride layer, and a silicon oxide layer are formed on a cured organopolysiloxane, but it is insufficient as a water vapor transmission rate for an electronic device. Also, bending resistance was insufficient.

JP 2008-159824 A JP 2010-36577 A

  An object of the present invention is to provide a uniform film that can achieve both barrier performance and bending resistance, and to apply the film to an element that requires barrier properties such as a substrate for organic electronic devices. .

  The object of the present invention is achieved by adopting the following configuration.

(1)
In a barrier film having at least one organic layer on a resin substrate, a first SiO _x (x> 2) layer having a thickness of 5 to 150 nm is laminated on the organic layer, and the SiO _x (x> 2 And) a barrier film having at least two inorganic layers containing silicon atoms and oxygen atoms on the layer.

(2)
The barrier film according to (1), wherein a second SiO _x (x> 2) layer having a thickness of 1 to 10 nm is laminated also on the outermost layer side of the inorganic layer.

(3)
At least 1 layer contains the nitrogen atom among the said inorganic layers, The barrier film as described in (1) or (2) characterized by the above-mentioned.

(4)
The barrier film according to any one of (1) to (3), wherein the first SiO _x (x> 2) layer is 5 to 100 nm or less.

(5)
The barrier film according to any one of (1) to (4), wherein the first SiO _x (x> 2) layer is 5 to 50 nm or less.

(6)
At least one of the inorganic layers is obtained by applying polysilazane, and at least the uppermost inorganic layer of the inorganic layers is subjected to an oxidation treatment after application (1) to The barrier film according to any one of (5).

(7)
The barrier film according to (6), wherein the oxidation treatment is a treatment of irradiating a vacuum ultraviolet ray having a wavelength component of 180 nm or less.

(8)
The barrier film according to (7), wherein the treatment of irradiating the vacuum ultraviolet ray is performed in an atmosphere having an oxygen concentration of 0.001 to 5%.

(9)
(1)-(8) The organic electronic device characterized by using the barrier film of any one of (8).

  According to the present invention, a uniform film capable of achieving both barrier performance and bending resistance can be provided, and the film can be applied to an element that requires barrier properties such as a substrate for organic electronic devices.

It is an example of the basic composition of an organic electronic device. It is a schematic sectional drawing of the barrier film of this invention.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

<Barrier film>
First, the barrier film of the present invention will be described.

The barrier film of the present invention is a barrier film having at least one organic layer on a resin substrate, and a first SiO _x (x> 2) layer having a thickness of 5 to 150 nm is laminated on the organic layer. And having at least two inorganic layers containing silicon atoms and oxygen atoms on the SiO _x (x> 2) layer (for example, see FIG. 2 as a preferred embodiment).

The thickness of the first SiO _x (x> 2) layer is preferably 5 to 100 nm or less, and more preferably 5 to 50 nm or less because the water vapor barrier performance is further improved. The first SiO _x (x> 2) layer refers to an oxygen-excess state with respect to Si, and can be regarded as a silanol layer, for example. Although the detailed mechanism is unknown, in the present invention, when the first SiO _x (x> 2) layer that is oxygen-excess with respect to Si is laminated on the resin substrate side to be thicker than 150 nm, it is originally formed as a barrier layer. The inventors have found that the water vapor barrier property of the inorganic layer is deteriorated.

In the present invention, two or more inorganic layers containing silicon atoms and oxygen atoms are laminated. By making two or more inorganic layers, the first layer is affected by the oxygen-excess layer such as the first SiO _x (x> 2), but if it is two or more layers, the second and subsequent layers are oxygenated. This is because a film having a higher barrier property can be formed to reduce the influence of the excess layer. Further, when the inorganic layer contains nitrogen atoms, the water vapor barrier property is improved and the bending resistance can be improved.

The barrier film of the present invention preferably has a water vapor transmission rate measured according to the JIS K7129B method of 10 ⁻³ g / m ² / day or less, more preferably 10 ⁻⁴ g / m ² / day or less, still more preferably. Is 10 ⁻⁵ g / m ² / day or less.

It is preferable that the oxygen transmission rate is less than 0.01ml ^/ m 2 ^/ day, more preferably not more than 0.001ml ^/ m 2 ^/ day.

  Subsequently, each element constituting the present invention will be described.

<SiO _x (x> 2) layer>
The first SiO _x (x> 2) layer in the present invention can be formed, for example, by applying a liquid containing a silicon compound on the organic layer and then oxidizing it.

  The silicon compound is preferably an inorganic polymer having no organic group from the viewpoint of barrier properties.

The first SiO _x (x> 2) layer on the organic layer needs to have a thickness in the range of 5 to 150 nm or less, preferably 5 to 100 nm or less, more preferably 5 to 5 from the viewpoint of gas barrier properties. 50 nm or less.

In the present invention, it is preferred that the outermost layer side to the second _SiO x (x> 2) layer of the inorganic layer is present, the thickness of the _SiO x (x> 2) layer is below 1~10nm Preferably there is. More preferably, it is 1-5 nm or less. Here, the outermost layer side of the inorganic layer means the side farthest from the substrate of the nth inorganic layer when there are n inorganic layers.

The ratio of O and Si in the SiO _x (x> 2) layer in the present invention can be measured by measuring by XPS (X-ray Photoelectron Spectroscopy) while scraping the SiO _x (x> 2) layer by sputtering. The apparatus can be measured using, for example, ESCALab200R (manufactured by VG Scientific).

Further, it has been found by the inventors' studies that the presence of the first SiO _x (x> 2) layer on the organic layer improves the adhesion with the organic layer.

  Preferred silicon compounds that can be used in the present invention include perhydropolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, and dimethyldiethoxysilane. , Methyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane , Dimethyldivinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsila 3,3,3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, Diacetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxy Silane, diaryldimethoxysilane, butyldimethoxyvinylsilane, trimethyl-3-vinylthiopropylsilane Phenyltrimethylsilane, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3- Glycidoxypropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane , 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glyci Doxypropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, Divinylmethylphenylsilane, diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3- Glycidoxypropylmethylsilane, octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylpheny Silane, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,1 3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) ) Tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5 -Trimethylcyclotrisiloxane, octamethylcyclote La siloxane, 1,3,5,7-tetra-ethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may be mentioned decamethylcyclopentasiloxane like.

  Of these, the silicon compound preferably has no organic group, and perhydropolysilazane is more preferably used. In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added to the liquid containing the silicon compound.

  Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. When these are applied, in order to suppress the reaction between the coating solution and moisture, it is preferable to use a solvent that does not easily contain moisture, such as xylene, dibutyl ether, solvesso, turpentine, and the like.

<Inorganic layer>
The inorganic layer in the present invention is a layer containing silicon atoms and oxygen atoms, excluding the SiO _x (x> 2) layer. Moreover, it is preferable that the inorganic layer in this invention has a nitrogen atom.

  Specifically, an inorganic oxide having silicon is preferable as the constituent material, and a layer having silicon oxide, silicon oxynitride, or the like can be given.

In particular, the inorganic layer in the present invention preferably contains silicon oxynitride because the barrier property and bending resistance are improved. When the amount of nitrogen is SiO _x N _y , x is preferably 0.1 to 1.8 and y is preferably 0.3 to 1.0. More preferably, x is between 0.2 and 1.4.

  As a method for forming the inorganic layer, a vapor deposition method, a coating method, a physical vapor deposition method (PVD) such as a sputtering method or an ion plating method, a chemical vapor deposition method (CVD), a sol-gel method, or the like is used. However, the coating method is preferred from the viewpoints of productivity and smoothness.

  Among the inorganic layers in the present invention, at least one layer is preferably prepared by applying a coating liquid containing polysilazane. From the viewpoint of barrier properties, the inorganic layer (particularly the outermost inorganic layer) is preferably oxidized.

  Moreover, the inorganic layer in this invention has two or more layers on the organic layer on a resin substrate. As this aspect, for example, when the first inorganic layer and the second inorganic layer are sequentially stacked from the substrate side, or the first inorganic layer and the second inorganic layer In some cases, an organic layer or the like is provided between the layers.

(Coating film forming method)
Any appropriate method can be adopted as the coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The thickness of the formed inorganic layer is preferably 50 to 1 μm from the viewpoints of productivity and barrier properties. A more preferable thickness is 40 to 500 nm, still more preferably 40 to 300 nm.

  The applied film is preferably annealed. The annealing temperature is preferably 60 ° C to 200 ° C, more preferably 70 ° C to 160 ° C. The annealing time is preferably about 5 seconds to 24 hours, more preferably about 10 seconds to 2 hours. By performing annealing in such a range, a part of polysilazane reacts to immobilize molecules, and an inorganic layer having good characteristics can be obtained. The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). During annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 30% RH to 90% RH, more preferably 40% RH to 80% RH.

(Coating film of polysilazane-containing liquid)
The inorganic layer according to the present invention is preferably formed by applying at least one layer (particularly the outermost layer) with polysilazane and performing an oxidation treatment.

Any appropriate method can be adopted as a coating method of polysilazane. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. As a coating film thickness, it is preferable that the film thickness after drying is about 10 nm to 3 μm. It is preferable that the thickness of the first layer of the inorganic layer laminated on the first SiO _{x (x>} 2) layer is about 50 nm to 1 [mu] m, the thickness of the second layer or more inorganic layers Is preferably thinner than the first inorganic layer on the first SiO _x (x> 2) layer, and preferably about 30 nm to 500 nm. This is because the barrier property and the stability are improved within this range. In the present invention, the first inorganic layer counted from the substrate is the first inorganic layer, and the nth inorganic layer counted from the substrate in the following order is the nth inorganic layer.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and includes SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _{y made of} Si—N, Si—H, N—H, or the like. Such as a ceramic precursor inorganic polymer.

In the formula, each of R ₁ , R ₂ , and R ₃ independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or the like.

In the present invention, perhydropolysilazane in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as the resulting barrier film.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, thereby improving the adhesion to the base substrate. Furthermore, it is preferable because the ceramic film made of hard and brittle polysilazane can be tough, and even when the (average) film thickness is increased, the occurrence of cracks can be suppressed. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at a low temperature, silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with polysilazane of the above chemical formula 1 (Japanese Patent Laid-Open No. 5-238827), glycidol addition obtained by reacting glycidol Polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting a metal carboxylate 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (specialty) Kaihei 7-19 986 JP), and the like.

  Examples of the organic solvent for preparing a liquid containing polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, alicyclic ethers, etc. Ethers can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the target silica film thickness and the pot life of the coating solution.

  Polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. By having an alkyl group, particularly a methyl group having the smallest molecular weight, the adhesion to the base substrate can be improved, and a hard and brittle silica film can be toughened, and even if the film thickness is increased, cracks are not generated. Occurrence is suppressed.

  In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd.

(Oxidation treatment)
As oxidation treatment of polysilazane, steam oxidation and / or heat treatment (including drying treatment), treatment by ultraviolet irradiation, and the like are known. Among them, it is preferable to perform the treatment by irradiation with vacuum ultraviolet rays having a wavelength component of 180 nm or less having a higher photon energy. This is because the barrier property is enhanced by the vacuum ultraviolet irradiation.

(Treatment by vacuum ultraviolet radiation having a wavelength component of 180 nm or less)
In the present invention, a preferable method includes treatment by vacuum ultraviolet irradiation. The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm which is larger than the interatomic bonding force in the compound. This is a method of forming a film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting atoms directly by the action of only photons called photon processes.

In particular, in the treatment of a polysilazane film, when an excimer irradiation treatment is performed after a single layer is applied, two or more continuous modified layers may be formed (this is why the present inventors have SiO _x (x> 2) layers. + Inorganic layer). In that case, the film thickness of the SiO _x (x> 2) layer can be controlled by changing the excimer irradiation processing time. Although the mechanism is not clear, the present inventors proceeded simultaneously with the direct cleavage of the silazane compound by light energy and the surface oxidation reaction by active oxygen and ozone generated in the gas phase, and the moisture on the organic layer, etc. It is estimated that it will be in such a state.

  A rare gas excimer lamp is preferably used as a vacuum ultraviolet light source required for vacuum ultraviolet irradiation.

Since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded and do not form molecules, they are called inert gases. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  According to the study by the present inventors, the oxygen concentration is preferably 0.001 to 5% as the environment during the excimer irradiation treatment. Furthermore, if it is 0.01 to 3%, performance is stable and preferable. This is because the productivity is improved and the oxidation treatment is sufficient when the amount is within this range. As for the stage temperature, it is preferable to apply heat to advance the reaction. In this case, the temperature is preferably 50 ° C. or more and Tg or less of the base material because the reactivity is improved without damaging the base material.

(Organic layer)
The organic layer according to the present invention flattens the rough surface of the transparent resin substrate where protrusions and the like exist, in addition to the purpose of relieving stress against bending of the barrier film, or is transparent by the protrusions existing on the transparent resin substrate. It is provided to fill and flatten irregularities and pinholes generated in the inorganic compound layer. Such an organic layer is preferably formed by, for example, applying and drying a composition containing a photosensitive resin, followed by curing. The basic skeleton of the components constituting the organic layer contains carbon, hydrogen, oxygen, nitrogen, sulfur and the like.

  As the photosensitive resin of the organic layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  The composition of the photosensitive resin contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, mihi -Ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, Examples include a combination of a photoreductive dye such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. Moreover, these photoinitiators can be used 1 type or in combination of 2 or more types.

  The method for forming the organic layer is not particularly limited, but it is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method.

  In the formation of the organic layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. Further, in any organic layer, an appropriate resin or additive may be used for improving the film forming property and preventing the generation of pinholes in the film regardless of the position of the organic layer.

  Solvents used when forming an organic layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  For the smoothness of the organic layer, the maximum cross-sectional height Rt (p) is preferably 30 nm or less as a value expressed by the surface roughness specified by JIS B 0601. The maximum cross-sectional height Rt (p) can be measured, for example, with an AFM (atomic force microscope). Specifically, it is calculated from the cross-sectional curve of the unevenness continuously measured by a detector having a stylus with a minimum tip radius by AFM, and is measured many times in a section where the measurement direction is 30 μm with a stylus with a minimum tip radius. It is possible to measure the average roughness related to the amplitude of fine irregularities and to measure the maximum cross-sectional height.

  The thickness of the organic layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. When the thickness is 1 μm or more, the smoothness of the film having an organic layer can be easily improved, and when the thickness is 10 μm or less, the balance of optical properties of the film can be easily adjusted.

(Resin base material)
As the resin substrate used in the present invention, a flexible resin sheet or film that can be wound in a roll shape is suitable. Examples of the resin used for the resin base include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, and partially hydrolyzed vinyl chloride-vinyl acetate copolymer. , Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose acetate butyrate Copolymerization of cellulose derivatives such as rate resins, maleic acid and / or acrylic acid Acrylate copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal Resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin and other rubber-based resins, Examples thereof include, but are not limited to, silicone resins and fluorine resins. The thickness of the resin substrate is 50 to 300 μm, preferably 70 to 180 μm.

(Organic electronic device configuration)
An example of the basic configuration of the organic electronic device of the present invention is shown in FIG. As shown in FIG. 1, the organic electronic device of the present invention has a first electrode (11) and a second electrode (12) facing each other on a substrate (10) as basic components. At least one organic functional layer (13) is provided between the first electrode (11) and the second electrode (12).

  Examples of the organic functional layer (13) include an organic light emitting layer, an organic photoelectric conversion layer, and a liquid crystal polymer layer without any particular limitation. However, the present invention provides an organic light emitting device in which the functional layer is a thin film and is a current-driven device. This is particularly effective when the layer is an organic photoelectric conversion layer. Furthermore, the barrier film of the present invention is suitable for an organic EL device using an organic light emitting layer that requires the most barrier property among devices.

(Sealing)
The case where the barrier film of the present invention is applied as an organic electronic device will be described.

  First, on the second inorganic layer of the barrier film of the present invention, for example, in the case of an organic EL device, various types such as an anode layer / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode layer, etc. A functional layer made of an organic compound is prepared. The whole or upper part of the obtained organic EL element is sealed.

Examples of the sealing member include the barrier film of the present invention, polyethylene terephthalate, polycarbonate, polystyrene, nylon, polyvinyl chloride, and the like, and composites thereof, glass, and the like. In this case, as in the case of the resin substrate, a laminate of gas barrier layers such as aluminum, aluminum oxide, silicon oxide, and silicon nitride can be used. The gas barrier layer can be formed by sputtering, vapor deposition or the like on both surfaces or one surface of the sealing member before molding the sealing member, or may be formed on both surfaces or one surface of the sealing member after sealing by a similar method. . Also in this case, the oxygen permeability is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 X10 ⁻³ g / (m ² · 24 h) or less is preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Moreover, the structure of the compound used for an Example is shown below.

Example 1
<Preparation of barrier film 1>
(Resin base material)
As a resin base material, a 125 μm thick polyester film (Tetron O3 (trade name) manufactured by Teijin DuPont Films Ltd.) with easy adhesion on both sides is annealed at 170 ° C. for 30 minutes. It was.

(Formation of organic layer)
On the resin base material, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied and applied with a wire bar so that the (average) film thickness after drying was 4 μm. Thereafter, drying was performed at 80 ° C. for 3 minutes, and a high pressure mercury lamp was used in an air atmosphere. Curing conditions were cured at 1.0 J / cm ² to form a smooth layer.

  The maximum cross-sectional height Rt (p) at this time was 16 nm.

  The maximum cross-sectional height Rt (p), which is an index of surface roughness, is calculated by measuring 30 times within a 30 μm measuring section with a stylus having a minimum tip radius using an AFM (Atomic Force Microscope). did.

(Formation of first SiO _x (x> 2) layer)
On the organic layer, a dibutyl ether solution of perhydropolysilazane (PHPS) containing a low-temperature curable catalyst (solid content 20% by mass, manufactured by AZ Electronic Materials, trade name: Aquamica NAX120) is 140 nm by spin coating method. It was applied and dried so as to be, and stored at 60 ° C. and 90% for 1 hour to form a first SiO _x (x> 2) layer.

When observed by sputtering XPS, it was SiO _x (x = 2.1 to 2.3).

(Inorganic layer)
A dibutyl ether solution of perhydropolysilazane (PHPS) containing no catalyst on the first SiO _x (x> 2) layer (solid content 20% by mass, manufactured by AZ Electronic Materials, trade name: Aquamica NN320) is dried. The film is applied and dried by a two-layer spin coating method so that the film thickness of the subsequent first layer is 200 nm and the film thickness of the second layer is 100 nm, and is oxidized using the following vacuum ultraviolet ray processing apparatus and conditions. Went.

When the composition was confirmed by sputtering XPS,
The outermost surface of the second layer has a thickness of SiO _x (x = 2.15) of 5 nm, and the other portions are SiO _x N _y (x = 0.2-1, y = 0.3-0. 7).

The first layer was SiO _x N _y (x = 0.9 to 1.7, y = 0 to 0.6).

(Vacuum UV treatment equipment)
An excimer irradiation apparatus manufactured by M.D.Com Co., Ltd., wavelength 172 nm, lamp-filled gas Xe A sample fixed on the operating stage was subjected to a modification treatment under the following conditions.

(conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
5mm distance between sample and light source
Oxygen concentration in irradiation device 0.5%
Excimer irradiation time 30 seconds << Examples 2 and 3 >>
<Preparation of barrier films 2 and 3>
Barrier films 2 and 3 were produced in the same manner as in Example 1 except that when the first SiO _x (x> 2) layer was formed, the film thicknesses shown in Table 1 were used.

Example 4
<Preparation of barrier film 4>
The barrier film of Example 4 was produced by storing the barrier film of Example 3 under conditions of 60 ° C. and 90% RH for 3 hours. The layer of SiO _x (x> 2) on the outermost surface side was 20 nm.

Example 5
<Preparation of barrier film 5>
In forming the first inorganic layer in Example 3, a perhydropolysilazane dibutyl ether solution containing an amine catalyst (solid content 20% by mass, manufactured by AZ Electronic Materials, trade name: Aquamica NAX120) was used. A barrier film 5 was produced in the same manner as in Example 3 except that it was changed and stored at room temperature for 1 day to form a layer. The first layer was a SiO _x layer, where x = 1.98.

Example 6
<Preparation of barrier film 6>
A barrier film 6 was produced in the same manner as in Example 5 except that the oxygen concentration in the vacuum ultraviolet treatment of the second inorganic layer in Example 5 was changed to 10%. The second layer was a SiO _x layer, where x = 1.97.

Example 7
<Preparation of barrier film 7>
A barrier film 7 was produced in the same manner as in Example 6 except that the oxidation treatment of the second inorganic layer in Example 6 was not carried out by vacuum ultraviolet treatment but by UV ozone treatment for 1 hour. The second layer was a SiO _x layer, where x = 1.96.

Example 8
<Preparation of barrier film 8>
Further, on the barrier film of Example 5, a dibutyl ether solution of perhydropolysilazane (PHPS) containing no catalyst (solid content 20% by mass, manufactured by AZ Electronic Materials, trade name: Aquamica NN320) was formed with a film thickness of 50 nm. It applied so that it might become, and the oxidation process was performed using the vacuum ultraviolet-ray processing apparatus, and the barrier property film 8 was produced.

(conditions)
Excimer light intensity 60 mW / cm ² (172 nm)
5mm distance between sample and light source
Oxygen concentration in irradiation device 0.5%
Excimer irradiation time 30 seconds Third layer The outermost surface had a thickness of SiO _x (x = 2.15) of 5 nm.

The other part was SiO _x N _y (x = 0.2 to 1, y = 0.3 to 0.7).

Example 9
<Preparation of barrier film 9>
A barrier film 9 was produced in the same manner except that a silicon oxynitride layer (silicon oxynitride film) was formed on the second inorganic layer of Example 3 by the reactive ion plating method. The second layer was a SiO _x N _y layer.

Example 10
<Preparation of barrier film 10>
The first SiO _x (x> 2) layer on the organic layer of Example 6 was converted to a xylene solution of perhydropolysilazane containing an amine catalyst (solid content: 20% by mass, manufactured by AZ Electronic Materials, trade name: AQUAMICA NAX120 ) Was applied and dried so that the film thickness was 250 nm, and the film was treated for 3 days under the conditions of 60 ° C. and RH 90% to prepare a barrier film 10. When the above layer was confirmed by sputtering XPS, it was a layer of SiO _x (x = 2.2). Otherwise, the barrier film 10 was prepared in the same manner as in Example 6.

Example 11
<Preparation of barrier film 11>
In the same manner as in Example 1, after forming the first SiO _x (x> 2) layer on the organic layer, the first inorganic layer described in Example 10 was formed to form the barrier film 11. Was made.

Example 12
Using the first SiO _x (x> 2) layer on the organic layer of Example 1 and forming the first inorganic layer using the second layer manufacturing method of Example 9, barrier properties Film 12 was produced.

(Evaluation methods)
(Evaluation of water vapor transmission rate)
The following measurement methods were used for evaluation.

Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Preparation of cell for evaluating water vapor barrier property A portion (12 mm) of a barrier film sample to be vapor-deposited before applying a transparent conductive film using a vacuum vapor deposition device (vacuum vapor deposition device JEE-400 manufactured by JEOL Ltd.) Other than 9 x 12 mm masks, metal calcium was vapor-deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. In addition, in order to confirm the change in the gas barrier property before and after bending, a water vapor barrier property evaluation cell was similarly prepared for the barrier film which was not subjected to the bending treatment.

  The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.

  In addition, in order to confirm that there is no permeation of water vapor other than from the barrier film surface, instead of the barrier film sample as a comparative sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm, The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

  The obtained water content was classified into the following five stages.

Less than 5: 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more and less than 5 × 10 ⁻⁴ g / m ² / day 3: 5 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more (Smoothness (surface roughness))
The maximum cross-sectional height Rt (p), which is an index of surface roughness, is a cross-section of irregularities continuously measured with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope; DI3100 manufactured by Digital Instruments). It was calculated from the curve, measured 30 times in a section with a measuring direction of 30 μm with a stylus with a very small tip radius, and obtained from the average roughness regarding the amplitude of fine irregularities.

○: Less than 5 nm Δ: 5 nm or more and less than 10 nm ×: 10 nm or more (barrier property after bending (bending resistance))
The water vapor permeability of a sample that was bent 100 times at an angle of 180 degrees was evaluated so that the curvature was 10 mm in radius, and the degree of deterioration from the sample that was not bent was evaluated.

Water vapor transmission rate after bending test / Water vapor transmission rate without bending (%)
◎: 90% or more ○: 80% or more and less than 90% △: 60% or more and less than 80% ×: less than 60%

Example 2
<< Production of Organic Electronic Device (Organic EL Element) 101 >>
<Formation of first electrode layer>
A 120-nm-thick ITO (indium tin oxide) film was formed by sputtering on the inorganic layer of the barrier film 1 produced in Example 1, and patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.

<Formation of hole transport layer>
On the 1st electrode layer of the barrier film 1 in which the 1st electrode layer was formed, after apply | coating the coating liquid for positive hole transport layer formation shown below with an extrusion coater, it dried and formed the positive hole transport layer. . The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before coating the hole transport layer forming coating solution, the cleaning surface modification treatment of the barrier film 1 was performed using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. . The charge removal treatment was performed using a static eliminator with weak X-rays.

(Application conditions)
The coating process was performed in the atmosphere at 25 ° C. and a relative humidity of 50%.

(Preparation of coating solution for hole transport layer formation)
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

(Drying and heat treatment conditions)
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

<Formation of light emitting layer>
Subsequently, on the hole transport layer of the barrier film 1 formed up to the hole transport layer, the following white light emitting layer forming coating solution was applied by an extrusion coater and then dried to form a light emitting layer. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

(Coating liquid for white light emitting layer formation)
The host material HA is 1.0 g, the dopant material DA is 100 mg, the dopant material DB is 0.2 mg, the dopant material DC is 0.2 mg, and dissolved in 100 g of toluene to form a white light emitting layer. It was prepared as a coating solution.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

(Drying and heat treatment conditions)
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., followed by a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

<Formation of electron transport layer>
Subsequently, after forming the light emitting layer, the following coating liquid for forming an electron transport layer was applied by an extrusion coater and then dried to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

(Coating liquid for electron transport layer formation)
The electron transport layer was prepared by dissolving EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.

(Drying and heat treatment conditions)
After applying the coating solution for forming the electron transport layer, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
Subsequently, an electron injection layer was formed on the formed electron transport layer. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Subsequently, the second electrode forming material is formed on the formed electron injection layer under a vacuum of 5 × 10 ⁻⁴ Pa except for the portion that becomes the take-out electrode on the first electrode on the formed electron injection layer. A mask pattern was formed by vapor deposition so that a light emitting area was 50 mm square by using aluminum as an extraction electrode, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The barrier film 1 formed up to the second electrode was moved again to a nitrogen atmosphere and cut into a prescribed size to produce an organic EL device.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm, surface Treated NiAu plating).

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
A sealing member was bonded to the organic EL element to which the electrode lead (flexible printed circuit board) was connected using a commercially available roll laminating apparatus, and the organic EL element 101 was manufactured.

  In addition, as a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), a polyethylene terephthalate (PET) film (12 μm thick) with an adhesive for dry lamination (two-component reaction type urethane adhesive). The laminate used (adhesive layer thickness 1.5 μm) was used.

  A thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct-based curing accelerator After that, the sealing substrate is closely attached and arranged so as to cover the joint portion of the take-out electrode and the electrode lead, and pressure bonding conditions using the pressure roll, pressure roll temperature 120 ° C., pressure 0. Close sealing was performed at 5 MPa and an apparatus speed of 0.3 m / min.

<< Production of organic EL elements 102 to 111 >>
In the production of the organic EL element 101, the organic EL elements 102 to 111 were produced using the barrier films 2 to 11 instead of the barrier film 1.

<< Evaluation of organic EL elements >>
The obtained organic EL elements 101 to 111 were stored at 60 ° C. and 90% RH for 300 hours and compared with the state before storage.

(Spot evaluation method)
A current of 1 mA / cm ² was applied to the sample to emit light, and a part of the panel was magnified with a 100 × microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200), and photographing was performed. The photographed image was cut out in a 2 mm square and visually observed to examine the situation of black spots.

A: No degradation is observed from 0 to 300 hours B: Slight degradation is observed from 0 to 300 hours C: Degradation is observed from 0 to 300 hours, but there is no practical problem D: From 0 hours to 300 hours, the level is a problem with practically significant deterioration.

(High temperature and high humidity storage)
Changes in light emission luminance when each organic EL element is stored at 60 ° C. and 90% relative humidity for 300 hours and then driven at a constant current of ^2.5 mA / cm ^2. Was measured and compared with each characteristic of each untreated organic EL element, and high temperature and high humidity storage stability was evaluated according to the following criteria. For the measurement, voltage / current generation / measurement device R6243 manufactured by ADC Co., Ltd. was used as the driving power source, and a spectral radiance meter CS-2000 manufactured by Konica Minolta Sensing Co., Ltd. was used as the luminance measurement device.

A: Luminance variation at a constant current density is less than 5% for untreated products B: Luminance variation at a constant current density is 5% or more and less than 10% for untreated products C: Untreated The brightness fluctuation when the current density is constant is 10% or more.

  From Table 2, it was found that when a film having a high barrier property was used, there were fewer dark spots and luminance variations were smaller than in the comparative example.

10 substrate 11 first electrode 12 second electrode 13 organic functional layer 20 resin substrate 21 organic layer 22 first _SiO x (x> 2) layer 23 inorganic layer 24 second _SiO x (x> 2) layer

Claims (9)

In a barrier film having at least one organic layer on a resin substrate, a first SiO _x (x> 2) layer having a thickness of 5 to 150 nm is laminated on the organic layer, and the SiO _x (x> 2 And) a barrier film having at least two inorganic layers containing silicon atoms and oxygen atoms on the layer. The barrier film according to claim 1, wherein a second SiO _x (x> 2) layer having a thickness of 1 to 10 nm is also laminated on the outermost layer side of the inorganic layer.   The barrier film according to claim 1 or 2, wherein at least one of the inorganic layers contains a nitrogen atom. The barrier film according to claim 1, wherein the first SiO _x (x> 2) layer is 5 to 100 nm or less. The barrier film according to claim 1, wherein the first SiO _x (x> 2) layer is 5 to 50 nm or less.   At least one of the inorganic layers is obtained by applying polysilazane, and at least the uppermost inorganic layer of the inorganic layers is subjected to an oxidation treatment after application. 6. The barrier film according to any one of 5 above.   The barrier film according to claim 6, wherein the oxidation treatment is a treatment of irradiating a vacuum ultraviolet ray having a wavelength component of 180 nm or less.   The barrier film according to claim 7, wherein the treatment of irradiating the vacuum ultraviolet ray is performed in an atmosphere having an oxygen concentration of 0.001 to 5%.   An organic electronic device using the barrier film according to claim 1.

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