JP2009090633A - GAS BARRIER FILM, MANUFACTURING METHOD THEREOF, AND ELECTRONIC DEVICE USING GAS BARRIER FILM - Google Patents

Abstract

A gas barrier film having high barrier performance is provided.
A gas barrier film having at least one organic layer, at least one inorganic layer, and at least one water catching layer on a base film.
[Selection figure] None

Description

  The present invention relates to a gas barrier film, a method for producing the same, and an electronic device using the gas barrier film.

  Conventionally, a gas barrier film in which a water capturing layer is provided on a gas barrier layer made of an inorganic layer is known (Patent Document 1, Patent Document 2). However, when these gas barrier films are used in an electronic device, the high water vapor barrier performance necessary for the electronic device cannot be obtained.

JP-A-10-329256 JP-A-7-321365

The object of the present invention is to provide a gas barrier film having a high barrier performance.
Further, as a result of studies by the present inventors, it was found that in a gas barrier film in which a water barrier layer is provided on a gas barrier layer made of an inorganic layer, interfacial peeling occurs due to bending or the like, and the barrier properties deteriorate. Then, it aims at providing the gas barrier film which eliminated this problem.

As a result of intensive studies by the present inventors based on the above problems, the gas barrier layer is an organic-inorganic laminated type having at least one organic layer and at least one inorganic layer, and further, a water catching layer is provided. It has been found that the barrier property is improved by the provision. Furthermore, it was found that by providing a water catching layer adjacent to the organic layer, the adhesion at the interface of each layer is improved, so that interface peeling due to bending or the like can be suppressed. The present invention has been accomplished based on such findings, and specifically has been achieved by the following means.
(1) A gas barrier film having at least one organic layer, at least one inorganic layer, and at least one water catching layer on a base film.
(2) The gas barrier film according to (1), wherein the water capturing layer is not the outermost layer.
(3) The gas barrier film according to (1) or (2), wherein the water capturing layer is a layer formed by dispersing a hygroscopic material in a resin.
(4) The gas barrier film according to (1) or (2), wherein the water capturing layer is a layer made of a hygroscopic polymer.
(5) The gas barrier film according to any one of (1) to (4), wherein at least one surface of the water capturing layer is adjacent to the organic layer.
(6) The gas barrier film according to any one of (1) to (4), wherein both surfaces of the water capturing layer are adjacent to the organic layer.
(7) The gas barrier film according to any one of (1) to (4), wherein the gas barrier film has a structure in which an inorganic layer, an organic layer, a water catching layer, and an organic layer are adjacently laminated.
(8) The gas barrier according to any one of (1) to (4), wherein a structure in which an inorganic layer, an organic layer, a water capturing layer, and an organic layer are adjacently laminated is repeated two or more units. the film.
(9) A method for producing a gas barrier film according to any one of (1) to (8), wherein a hygroscopic material is dispersed in a resin to provide a water capturing layer. Method.
(10) The method for producing a gas barrier film according to any one of (1) to (8), wherein the hygroscopic material is dispersed in a polymer binder resin, or an electron beam or an ultraviolet curable resin to capture water. A method for producing a gas barrier film, comprising providing a layer.
(11) An electronic device having the gas barrier film according to any one of (1) to (8).
(12) The electronic device according to (11), wherein the electronic device is an organic EL element, a solar cell, a touch panel, or electronic paper.
(13) A method for producing an electronic device, wherein the gas barrier film according to any one of (1) to (8) is used as a sealing film or a substrate.

  According to the present invention, it is possible to provide a gas barrier film with improved barrier properties. Furthermore, in the case of stacking a plurality of organic, inorganic, and water catching layers, by providing a water catching layer adjacent to the organic layer, the unevenness caused by the dispersion in the water catching layer can be flattened by the organic layer. Since the barrier property of the inorganic layer provided on the substrate is improved, it is possible to provide a gas barrier film in which an organic layer, an inorganic layer, and a water trapping layer having a very high barrier property are laminated.

  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. The organic EL element in the present invention refers to an organic electroluminescence element.

The gas barrier film of the present invention is characterized by having at least one organic layer, at least one inorganic layer, and at least one water catching layer on the base film. Thus, by having a water capturing layer, it is possible to suppress element deterioration due to moisture at the time of manufacturing an electronic device. In the present invention, the water catching layer is preferably not the outermost layer. By setting it as such a structure, water catching can be raised more.
Moreover, it is preferable that at least one surface of the water catching layer is adjacent to the organic layer. By setting it as such a structure, the adhesiveness of a water catching layer and an organic layer increases, and even if there exists deformation | transformation, such as a bending, the high barrier property can be maintained. In particular, by providing an inorganic layer, an organic layer, and a water catching layer adjacent to each other in this order, the inorganic layer and the water catching layer are provided via an organic layer having good adhesion. The adhesiveness at the interface is remarkably increased as compared with the case where the adjacent layers are provided. In addition, it is preferable that the water catching layer is adjacent to the organic layer on the side far from the base film because the layer to be laminated next can be easily laminated. That is, although the surface may be uneven depending on the type of the water capturing layer, the uneven surface can be substantially eliminated by providing an organic layer on the uneven surface. This configuration is particularly useful when the next layer to be laminated is an inorganic layer. In addition, this configuration has an advantage that moisture entering from the cross section of the organic layer can be captured by the water capturing layer. Furthermore, in the present invention, a configuration in which both sides of the water capturing layer are adjacent to the organic layer is more preferable. The above effects are exhibited synergistically and the barrier properties are remarkably improved.
The gas barrier film of the present invention preferably has a structure in which an inorganic layer, an organic layer, a water capturing layer, and an organic layer are adjacently laminated in this order, and it is more preferable that the structure repeats two or more units. By adopting such a configuration, higher barrier properties can be obtained. In particular, the outermost (the farthest from the base film) water catching layer penetrates into the film by repeating two or more units of an inorganic layer, an organic layer, a water catching layer, and an organic layer laminated in order. Plays a role in capturing moisture.
Moreover, in this invention, the above laminated structures may be provided only on one side of the base film, or may be provided on both sides. The barrier performance can be further improved by providing both surfaces.

 Here, the organic layer and the inorganic layer constitute a so-called gas barrier layer having a function of blocking oxygen and moisture in the atmosphere by being laminated. Therefore, it is preferable that the organic layer and the inorganic layer are alternately laminated. In addition, a so-called gradient material layer in which the composition of the organic layer and the inorganic layer continuously changes in the film thickness direction may be used without departing from the spirit of the present invention. Examples of the gradient materials include a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. , American Vacuum Society) ”, or a continuous layer in which the organic layer and the inorganic layer do not have an interface as disclosed in US Published Patent Application No. 2004-46497.

The preferable layer structure of the gas barrier film of this invention is illustrated below. Needless to say, the gas barrier film of the present invention is not limited thereto.
Base film / organic layer / inorganic layer / water catching layer base film / organic layer / inorganic layer / organic layer / water catching layer base film / organic layer / inorganic layer / organic layer / water catching layer / inorganic layer base material Film / organic layer / inorganic layer / organic layer / water catching layer / organic layer / inorganic layer substrate film / organic layer / inorganic layer / organic layer / water catching layer / organic layer / inorganic layer / organic layer / water catching layer / Organic Layer / Inorganic Layer In addition, the gas barrier film of the present invention may contain other constituent layers within the scope of the present invention. Other constituent layers include a light extraction improving layer (lens layer) (for example, one described in JP-A-9-171892), a prism layer (for example, one described in JP-A-2003-86353), scattering, and the like. Layer (backscattering) (for example, described in JP-A-2003-332065), diffusion layer (for example, described in JP-A-9-50031), polarizing layer (for example, JP-A-7-142170) As well as matting agent layers, protective layers, antistatic layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, antifouling layers, printing layers, etc. It is done.

(Capture layer)
The water trapping layer in the present invention is not particularly defined as long as it is a layer satisfying the ability to catch water vapor and keep it in the layer, and is preferably a layer whose dimensional change due to water vapor trapping is small. Such a water capturing layer is, for example, a layer obtained by dispersing a hygroscopic polymer layer or a hygroscopic material in the resin, and from the viewpoint of further improving the accuracy of the electronic device, the hygroscopic material is used as the resin. A layer obtained by dispersing is preferable.
Here, polyamide etc. are mentioned as a hygroscopic polymer. Examples of the hygroscopic material include silica gel, aluminum oxide, and magnesium oxide, and anhydrous barium sulfate and barium oxide are preferable. Examples of the resin include a polymer binder resin, or an electron beam or an ultraviolet curable resin, and examples of the polymer binder resin include PVA, EVOH, polyethylene, polypropylene, PET, PEN, and PES, and an electron beam or an ultraviolet curable resin. Examples of the resin include methacrylate and acrylate. Examples of the dispersion medium include acetone, methanol, ethanol, isopropanol, and methyl ethyl ketone. Here, in the above-mentioned patent document 1 (Japanese Patent Laid-Open No. 10-329256), the water catching layer in Example 1 is obtained by dispersing anhydrous sodium sulfate in an acrylic resin. End up. Therefore, even if an inorganic layer is further formed thereon, only a gas barrier film having a low barrier property can be obtained. However, in the present invention, since the surface is smoothed by further providing an organic layer on the water capturing layer, the inorganic layer formed thereon exhibits a high barrier property. Moreover, in the said patent document 2 (Unexamined-Japanese-Patent No. 7-321365), in the Example, although the surface of the gas barrier layer (EVOH) is roughened and the water catching layer (nylon-6) is laminated, The present invention is significant in that such labor is unnecessary.
The thickness of the water capturing layer is not particularly defined, but is preferably 1 to 3 μm.

(Base film)
The barrier film substrate in the present invention usually uses a plastic film as a base film. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specifically, as the plastic film, metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin , Polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin Examples thereof include thermoplastic resins such as filn copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the barrier film substrate of the present invention is used as a substrate of a device such as an organic EL element described later, the plastic film is preferably made of a material having heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate ( PAr: 210 ° C., polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Japanese Patent Application Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the barrier film substrate of the present invention is used in combination with a polarizing plate, it is preferable that the barrier laminate of the barrier film substrate faces the inside of the cell and is arranged on the innermost side (adjacent to the element). . At this time, since the barrier film substrate is disposed inside the cell from the polarizing plate, the retardation value of the barrier film substrate is important. The usage form of the barrier film substrate in such an embodiment is as follows: a barrier film substrate using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate)) + Linear polarizing plate) are used in combination, or a linear polarizing plate is used in combination with a barrier film substrate using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate. Is preferred.

As a base film having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR Co., Ltd.) ): Arton, Nippon Zeon Co., Ltd .: Zeonoa), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd.): U100 (pellet) )), Transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

Since the barrier film substrate of the present invention is used as a device such as an organic EL element, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90. % Or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the barrier film substrate of the present invention is used for display applications, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The thickness of the plastic film used for the barrier film substrate of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

(Inorganic layer)
The inorganic layer is usually 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. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. The described forming method can be employed.
The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but for example, one or more selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, or the like An oxide containing metal, nitride, carbide, oxynitride, oxycarbide, nitride carbide, oxynitride carbide, or the like can be used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride, or oxynitride of Si or Al is particularly preferable. . These may contain other elements as secondary components.
Although it does not specifically limit regarding the thickness of the said inorganic layer, It is preferable to exist in the range of 5 nm-500 nm, More preferably, it is 10 nm-200 nm. Two or more inorganic layers may be laminated. In this case, each layer may have the same composition or a different composition. The number of inorganic layers is preferably 2 to 5 layers.

(Organic layer)
The organic layer is usually a polymer layer. Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, polysiloxane, other organic It is a layer of a silicon compound. The organic layer may consist of a single material or a mixture. Two or more organic layers may be laminated. In this case, each layer may have the same composition or a different composition. The total number of organic layers can be determined according to the total number of inorganic layers and the like. For example, when the inorganic layer has 2 to 5 layers, the organic layer has 3 to 9 layers.

The organic layer is preferably smooth and has a high film hardness. The smoothness of the organic layer is preferably 10 nm or less, and more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm square. The film hardness of the organic layer preferably has a pencil hardness of HB or higher, and more preferably H or higher.
The film thickness of the organic layer is not particularly limited, but if it is too thin, it will be difficult to obtain film thickness uniformity, and if it is too thick, cracks will be generated by external force and the barrier performance will deteriorate. From this viewpoint, the thickness of the organic layer is preferably 10 nm to 2000 nm, more preferably 100 nm to 1000 nm.

 Examples of the method for forming the organic layer include a normal solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294. It can apply | coat by the extrusion-coating method which uses-. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable. In the present invention, a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in Japanese Patent Application Laid-Open Nos. 2000-323273 and 2004-25732 may be used. Alternatively, a polymer layer may be formed by polymerizing a polymer precursor (for example, a polymerizable compound) and then polymerizing it.

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

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

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

(Use of gas barrier film)
The gas barrier film in the present invention can be preferably used for an electronic device. In particular, it is preferably used as a sealing film or substrate for electronic devices. Examples of the electronic device include an organic EL element, a solar cell, a touch panel, and electronic paper.

Organic EL element An organic EL element means an organic electroluminescence element. The gas barrier film in this invention becomes a sealing film of an organic EL element. The organic EL element has a cathode and an anode on a substrate, and an organic compound layer including a light emitting layer between both electrodes. Due to the nature of the light emitting element, at least one of the anode and the cathode is transparent.

 As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.

Next, each element which comprises an organic EL element is demonstrated in detail.
Substrate The substrate used for the organic EL device in the present invention may be the gas barrier film of the present invention or a substrate used for a known organic EL device. The organic EL substrate may be a resin film or a gas barrier film. In the case of a gas barrier film, in addition to the gas barrier film of the present invention, the gas barrier film described in JP-A No. 2004-136466, JP-A No. 2004-148766, JP-A No. 2005-246716, JP-A No. 2005-262529, etc. Can also be preferably used.

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

Anode The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. Thus, it can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode. The transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Electrode Film” published by CMC (1999). When using a plastic substrate with low heat resistance as the substrate, ITO or IZO is used, and a transparent anode formed at a low temperature of 150 ° C. or lower is preferable.

Cathode The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials.

 Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, a material mainly composed of aluminum is preferable.
The material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The cathode material is described in detail in JP-A-2-15595 and JP-A-5-121172. Further, a dielectric layer made of a fluoride or oxide of an alkali metal or a Group 2 metal may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

The light-emitting layer organic EL device has at least one organic compound layer including a light-emitting layer, and as the organic compound layer other than the organic light-emitting layer, as described above, a hole transport layer, an electron transport layer, a charge Examples of the layer include a block layer, a hole injection layer, and an electron injection layer.

-Organic light emitting layer-
The organic light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, and receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines the holes and electrons. It is a layer having a function of providing light and emitting light. The light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of the fluorescent light-emitting material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyralidine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Typical examples include ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives. Various metal complexes are, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

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

  Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.

  Examples of the host material contained in the light emitting layer include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. And materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. In addition, the electron transport layer / electron injection layer may also function as a hole blocking layer.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
In addition, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer / hole injection layer may also serve this function.

  The solar cell can be applied to the one described in Japanese Patent Application No. 7-160334. The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like. The electronic paper can be applied to the one described in JP 2000-98326 A.

  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.

Preparation of Gas Barrier Film Gas barrier films having the layer structures of Examples 1 to 5 and Comparative Examples 1 and 2 shown in Table 1 below were prepared.
(Base film)
As the base film, a polyethylene naphthalate (PEN, thickness 100 μm, manufactured by Teijin DuPont Co., Ltd., Q65A) film was used.

(Formation of organic layer)
As a photopolymerizable acrylate, 9 g of tripropylene glycol diacrylate (TPGDA, manufactured by Daicel-Cytec) and 0.1 g of a photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 907) were dissolved in 190 g of methyl ethyl ketone, did. This coating solution is applied to a base film using a wire bar, and an irradiance is applied using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under a nitrogen purge with an oxygen concentration of 0.1% or less. An organic layer was formed by irradiation with ultraviolet rays at 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² . The film thickness was about 1000 nm.
In addition, when laminating the organic layer on the inorganic layer, the organic layer was formed by solvent coating immediately after the inorganic layer was formed.

(Formation of inorganic layer)
An inorganic layer of aluminum oxide was formed using a reactive sputtering apparatus. Specific film forming conditions are shown below.
The vacuum chamber of the reactive sputtering apparatus was evacuated to an ultimate pressure 5 × 10 ^-4 Pa by an oil rotary pump and a turbo molecular pump. Next, argon was introduced as a plasma gas, and power of 2000 W was applied from a plasma power source. A high-purity oxygen gas was introduced into the chamber, the film formation pressure was adjusted to 0.3 Pa, and the film was formed for a certain period of time to form an aluminum oxide inorganic layer. The obtained aluminum oxide film had a thickness of 40 nm and a film density of 3.01 g / cm ³ .
In addition, when laminating an inorganic layer on an organic layer, after depositing the organic layer by solvent coating, it is put in a vacuum chamber and depressurized, and after maintaining for a certain time in a state where the degree of vacuum is 10 ⁻³ Pa or less. An inorganic layer was formed.

(Formation of catchment layer)
In the coating solution prepared for the organic layer, anhydrous barium sulfate was dispersed as a water capturing agent so that the content in the film after forming the water capturing layer was 30% by weight. This coating solution was applied using a wire bar in the same manner as the organic layer, and then cured with ultraviolet rays to form a water catching layer having a thickness of 2000 nm.
Moreover, in Example 5, the layer which consists of nylon 6 was employ | adopted as a water capturing layer.

また、上記実施例１〜５および比較例１、２の層構成を図示したものを、図１に示した。図１中、１は基材フィルムを、２は有機層を、３は無機層を、４は捕水層を、５はナイロン６層をそれぞれ示している。

Moreover, what illustrated the layer structure of the said Examples 1-5 and Comparative Examples 1 and 2 was shown in FIG. In FIG. 1, 1 is a base film, 2 is an organic layer, 3 is an inorganic layer, 4 is a water catching layer, and 5 is a nylon 6 layer.

Evaluation of gas barrier film (interfacial adhesion (tape peeling method))
For the gas barrier film obtained above, a grid pattern method according to “JISK5400, paint general test method” (10 vertical and horizontal incisions are made at 1 mm intervals to make 100 1 mm square ridges, An evaluation method in which cellotape (registered trademark) was applied and then peeled off) was assigned a score in consideration of the number of cells peeled off and the peeled state (which interface was peeled off). Expressed in a five-step evaluation, 4 or more points were accepted. The results are shown in Table 2.

Preparation of Organic EL Element A conductive glass substrate having an ITO film (surface resistance value 10Ω / □) 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 3 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL device.

Attaching the gas barrier film to the organic EL element Using the thermosetting adhesive (Epotech 310, Daizonitomomori Co., Ltd.), the gas barrier film and the organic EL element substrate prepared in the above examples and comparative examples The adhesive was cured by bonding and heating at 65 ° C. for 3 hours so that the material film was on the outside. An organic EL element sealed in this way was produced.

Evaluation of Water Vapor Barrier Property of Organic EL Element The organic EL element obtained above was stored at 60 ° C. and 90% relative humidity, and the occurrence of dark spots was evaluated. The time until the area ratio of the dark spot was 5% or more was set to 3, 500 hours or more, 3, 250 hours to less than 500 hours, 2, or less than 250 hours 1. Two or more are practical levels. The results are shown in Table 2.

  As is clear from the above table, the organic EL device using the gas barrier film of the present invention was excellent in both adhesiveness and water vapor barrier property. In addition, although the polyamide layer of Comparative Example 3 is a water-absorbing polymer, it was found that swelling due to water absorption was large and it was not suitable for a precise element substrate.

It is the schematic which shows the layer structure of this-application Examples 1-5 and Comparative Examples 1 and 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 2 Organic layer 3 Inorganic layer 4 Water catching layer 5 Nylon 6 layer

Claims (13)

A gas barrier film having at least one organic layer, at least one inorganic layer, and at least one water catching layer on a base film. The gas barrier film according to claim 1, wherein the water capturing layer is not the outermost layer. The gas barrier film according to claim 1 or 2, wherein the water capturing layer is a layer formed by dispersing a hygroscopic material in a resin. The gas barrier film according to claim 1 or 2, wherein the water capturing layer is a layer made of a hygroscopic polymer. The gas barrier film according to claim 1, wherein at least one surface of the water capturing layer is adjacent to the organic layer. The gas barrier film according to any one of claims 1 to 4, wherein both surfaces of the water capturing layer are adjacent to the organic layer. The gas barrier film according to any one of claims 1 to 4, wherein the gas barrier film has a structure in which an inorganic layer, an organic layer, a water capturing layer, and an organic layer are laminated adjacently in this order. The gas barrier film according to any one of claims 1 to 4, wherein a structure in which an inorganic layer, an organic layer, a water capturing layer, and an organic layer are adjacently laminated is repeated two or more units. It is a manufacturing method of the gas barrier film of any one of Claims 1-8, Comprising: A hygroscopic material is disperse | distributed to resin and a water capturing layer is provided, The manufacturing method of the gas barrier film characterized by the above-mentioned. It is a manufacturing method of the gas barrier film of any one of Claims 1-8, Comprising: Disperse | distribute a hygroscopic material to a polymer binder resin, an electron beam, or an ultraviolet curable resin, and to provide a water capturing layer. A method for producing a gas barrier film. The electronic device which has a gas barrier film of any one of Claims 1-8. The electronic device according to claim 11, wherein the electronic device is an organic EL element, a solar cell, a touch panel, or electronic paper. A method for manufacturing an electronic device, comprising using the gas barrier film according to claim 1 as a sealing film or a substrate.

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