JP2006299145A - Gas barrier film, resin substrate using gas barrier film and used for organic electroluminescence and organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film which has a high gas barrier performance, does not deteriorate the performance even in high temperature high humidity environments, is suitable as a resin substrate for organic EL, and has an excellent gas barrier property. <P>SOLUTION: This gas barrier film having a gas barrier layer having a film density of ≥2 g/cm<SP>3</SP>on a resin film is characterized in that the gas barrier layer is formed by coating the resin film with a coating liquid, drying the coated liquid, and then subjecting the dried coating film to an energy treatment to give a high density. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a gas barrier film used as a plastic substrate for displays such as organic electroluminescence elements and liquid crystals, and an organic electroluminescence element using the gas barrier film.

  Conventionally, a gas barrier film in which a thin film of metal oxide such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is a packaging of articles that require blocking of various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.

  Aluminum foil is widely used as a packaging material in such fields, but disposal after use has become a problem, and it is basically opaque and the contents can be confirmed from the outside. In addition, the display material is required to be transparent and cannot be applied at all.

  On the other hand, a base material made of polyvinylidene chloride resin or a copolymer resin of vinylidene chloride and other polymers, or a material provided with gas barrier properties by coating these vinylidene chloride resins on polypropylene resin, polyester resin, or polyamide resin However, it is widely used as a packaging material. However, since chlorine gas is generated during the incineration process, it is a problem from the viewpoint of environmental protection. Can not be applied to the field where is required.

  In particular, transparent substrates, which are being applied to liquid crystal display elements, organic EL elements, etc., have recently been required to be lighter and larger, have long-term reliability and a high degree of freedom in shape, and have curved surface display. High demands such as being possible have been added, and film base materials such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken. For example, JP-A-2-251429 and JP-A-6-124785 disclose examples using a polymer film as a substrate of an organic electroluminescence element.

  However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to glass. For example, when used as a substrate of an organic electroluminescence element, if a base material with poor gas barrier properties is used, water vapor or air permeates and the organic film deteriorates, which becomes a factor that impairs light emission characteristics or durability. In addition, when a polymer substrate is used as a substrate for an electronic device, oxygen permeates the polymer substrate and permeates and diffuses into the electronic device, which deteriorates the device or is required in the electronic device. This causes a problem that the degree of vacuum cannot be maintained.

In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a gas barrier film substrate. Gas barrier films used for packaging materials and liquid crystal display elements are known in which silicon oxide is vapor-deposited on a plastic film (Patent Document 1) and in which aluminum oxide is vapor-deposited (Patent Document 2). At present, it has only a water vapor barrier property of about ² g / m ² / day or an oxygen permeability of about ² ml / m ² / day.

In recent years, due to the development of organic EL displays that require further gas barrier properties, large-sized liquid crystal displays, high-definition displays, etc., the gas barrier performance for film substrates is about 10 ^-3 g / m ² / day for water vapor barriers. Requests are rising.

  As a method to meet these demands for high water vapor barrier properties, a gas barrier film with a structure in which a dense ceramic layer and a flexible polymer layer that relieves impact from the outside are alternately laminated is proposed. (For example, see Patent Document 3). However, since the ceramic layer and the polymer layer generally have different compositions, the adhesion at each contact interface portion is deteriorated, which may cause quality deterioration such as film peeling. In particular, the deterioration of the adhesion appears remarkably under severe environments such as high temperature and high humidity or when irradiated with ultraviolet rays for a long period of time, and immediate improvement is required.

  Further, as a gas barrier film, Patent Document 4 discloses a composite film having a resin layer containing an inorganic layered compound and an organic-inorganic hybrid film by a sol-gel method.

In these composite films, when the gas barrier layer mainly composed of these metal oxides is formed from a metal compound by a sol-gel method, it is only formed by the hydrolysis and polycondensation process of the metal compound as described above. In the present situation where the demand for gas barrier properties is increasing, the gas barrier performance that can be said to be sufficient has not been achieved.
Japanese Patent Publication No.53-12953 JP 58-217344 A US Pat. No. 6,268,695 JP 2004-136466 A

  Accordingly, an object of the present invention is to provide a gas barrier film excellent in gas barrier properties, which is suitable as a resin substrate for organic EL, which has high gas barrier performance and does not significantly deteriorate in high temperature and high humidity environments. There is.

  The above object of the present invention is achieved by the following means.

(Claim 1)
A gas barrier film having a gas barrier layer having a film density of 2 g / cm ³ or more on a resin film, wherein the gas barrier layer is formed by applying a coating liquid and then drying and densifying by energy treatment. A gas barrier film characterized by that.

(Claim 2)
The gas barrier film according to claim 1, wherein the gas barrier layer is formed by applying and drying a coating liquid containing a metal alkoxide hydrolysis and polycondensation liquid.

(Claim 3)
3. The energy treatment according to claim 1, wherein any one of a corona discharge treatment, a plasma discharge treatment, and a flame plasma treatment is combined in addition to any one of ultraviolet treatment, electron beam treatment, and microwave treatment. Gas barrier film.

(Claim 4)
A resin substrate for organic electroluminescence, wherein a transparent conductive thin film is formed on the gas barrier film according to claim 1.

(Claim 5)
A phosphorescent light emitting organic electroluminescent material film and a metal film serving as a cathode are coated on the organic electroluminescent resin substrate according to claim 7, and a resin-laminated metal foil is further adhered and sealed with an adhesive. An organic electroluminescence element.

  According to the present invention, a gas barrier film having a high gas barrier property and good durability and suitable as a resin substrate for organic EL can be obtained.

  The structure of these gas barrier films will be described below.

  The composition of the gas barrier film in the present invention is not particularly limited as long as it is a layer that prevents permeation of oxygen and water vapor.

  The gas barrier film of the present invention is formed by applying a coating liquid, drying it, and densifying it by energy treatment.

  The gas barrier film of the present invention is formed by a so-called sol-gel method formed by a hydrolysis and polycondensation process of metal alkoxide which is a wet process.

  Therefore, specifically, an inorganic oxide is preferable as a material constituting the gas barrier film of the present invention, for example, silicon oxide, aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, tin oxide. Etc. can be mentioned.

  The present invention is characterized in that, for example, a metal oxide film formed by such a sol-gel method is subjected to energy treatment after drying.

As the energy treatment, the metal oxide film formed by the sol-gel method and dried is irradiated with active radiation at an irradiation intensity of 1 mJ / cm ^{2 to} 100 J / cm ² , preferably 10 mJ / cm ^{2 to} 10 J / cm ^2. Energy treatment, or treatment with active chemical species such as corona discharge or plasma discharge treatment, is performed.

  This energy treatment is considered to increase the density of the ceramic film formed by the sol-gel method and improve the gas barrier performance by taking a denser structure.

In the gas barrier film according to the present invention, the gas barrier film formed on the resin film is densified by energy treatment so that the film density is 2 g / cm ³ or more.

  As a result, the gas barrier film formed by applying a coating solution containing a sol-gel method, ie, hydrolysis of a metal alkoxide, polycondensation liquid, and drying is densified and becomes a dense film, which is high. Get gas barrier properties.

  In order to obtain high gas barrier properties, it is preferable to use two types of energy treatments together in the energy treatment.

  One is any one selected from ultraviolet treatment, electron beam treatment, and microwave treatment, and the other is any one selected from corona discharge treatment, plasma discharge treatment, and flame plasma treatment. It is. By combining these two types of energy treatment, a denser and denser film can be obtained.

  The ultraviolet treatment, electron beam treatment, and microwave treatment are treatments with actinic radiation and should be referred to as physical treatments. Therefore, it penetrates to some extent inside the membrane and affects the internal structure. For example, although an electron beam depends on energy, it penetrates to several μm from the surface and gives energy.

  On the other hand, corona discharge treatment, plasma discharge treatment, flame plasma treatment, and the like are treatments that should be called chemical treatments, and are surface treatments with high-energy chemical species. Therefore, it penetrates only to the vicinity of the surface pole.

  Accordingly, any one process selected from the above-mentioned ultraviolet treatment, electron beam treatment, and microwave treatment, which is a physical treatment, and any one process selected from corona discharge treatment, plasma discharge treatment, and flame plasma treatment, which are chemical treatments, are used in combination. Is preferable for increasing the density of the gas barrier film of the present invention obtained by the sol-gel method.

As the physical treatment, it is preferable to perform energy irradiation in the range of 1 mJ / cm ^{2 to} 100 J / cm ² , preferably 10 mJ / cm ^{2 to} 10 J / cm ² ,
Also, as chemical treatment, energy irradiation in the range of 1 mJ / cm ^{2 to} 100 J / cm ² , preferably 10 mJ / cm ^{2 to} 10 J / cm ² , may be performed, for example, an output of about 0.01 to 10 W / cm ^2. The ratio of the two types of energy treatment, which may be irradiated in the range of 0.1 seconds to several seconds, is not particularly limited, and varies depending on the composition, thickness, etc. of the film to which the energy treatment is applied. The two energy treatments only have to be performed substantially effectively within the above-mentioned ranges.

By performing such an energy treatment, using a gas barrier film formed by a sol-gel method, the water vapor transmission rate is 10 ⁻² g / m ² / day or less and the oxygen transmission rate is 10 ⁻² cc / cc. A gas barrier film of m ² / day or less can be obtained.

  In the present invention, the evaluation of gas barrier properties was performed using an oxygen permeability measuring device OX-TRAN2 / 21 · L type manufactured by Mocon and a water vapor permeability measuring device PERMATRAN-W3 / 33G type.

  The thickness of the gas barrier film in the present invention is appropriately selected depending on the type and configuration of the material used, and is suitably selected, but is preferably in the range of 5 to 2000 nm. This is because when the thickness of the gas barrier film is smaller than the above range, a uniform film cannot be obtained, and it is difficult to obtain a barrier property against gas. In addition, when the thickness of the gas barrier film is larger than the above range, it is difficult to maintain flexibility in the gas barrier film, and the gas barrier film is caused by external factors such as bending and pulling after film formation. This is because there is a risk that a crack will occur.

  The gas barrier film used in the present invention is a ceramic film formed by a sol-gel method using a metal alkoxide.

  The term “metal” in the metal alkoxide generally means “transition metals” elements, “lanthanoid” elements, “actinoid” elements in addition to “metals” defined in the periodic table, etc. , And boron as defined as “Non Metals”, including silicon (silicon), but preferred metal alkoxides used in the sol-gel method include alkoxysilanes and / or alkoxysilanes. Metal alkoxides can be used. As the metal alkoxide other than alkoxysilane, zirconium alkoxide, titanium alkoxide, aluminum alkoxide and the like are preferable.

  Examples of the alkoxysilanes include alkoxysilanes represented by the following general formula.

Si (OR ₁ ) _x (R ₂ ) _4-x
R ₁ in the above general formula is preferably an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. , Sec-butyl group, tert-butyl group, acetyl group and the like. R ₂ is preferably an organic group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl. Group, n-octyl group, tert-octyl group, n-decyl group, unsubstituted hydrocarbon group such as phenyl, vinyl group, allyl group, γ-chloropropyl group, CF ₃ CH ₂ —, CF ₃ CH ₂ CH _{2 -, C 2 F 5 CH} 2 CH 2 -, C 3 F 7 CH 2 CH 2 CH 2 -, CF 3 OCH 2 CH 2 CH 2 -, C 2 F 5 OCH 2 CH 2 CH 2 -, C 3 F ₇ OCH ₂ CH ₂ CH ₂ —, (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH ₂ —, C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ —, 3- (perfluorocyclohexyloxy) propyl, (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH _2- , H (C F ₂ ) Substituted hydrocarbon groups such as ₄ CH ₂ CH ₂ CH ₂ —, γ-glycidoxypropyl group, γ-mercaptopropyl group, 3,4-epoxycyclohexylethyl group, γ-methacryloyloxypropyl group, etc. . x is preferably an integer of 2 to 4.

  Specific examples of these alkoxysilanes are shown below.

  Examples of x = 4 include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-acetoxysilane and the like.

As x = 3, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso -Propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane Γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltri _{Tokishishiran, CF 3 CH 2 CH 2 Si} (OCH 3) 3, C 2 F 5 CH 2 CH2Si (OCH 3) 3, C 2 F 5 OCH 2 CH 2 CH 2 Si (OCH 3) 3, C 3 F 7 OCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 3- (perfluorocyclohexyloxy) propyltrimethoxysilane and the like.

As x = 2, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- iso- propyl dimethoxysilane, di -iso- propyl diethoxy silane, diphenyl dimethoxy silane, divinyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2Si (OCH 3) 2, (C 3 F 7 OCH 2 CH 2 CH 2 ) ₂ Si (OCH ₃ ) ₂ , [H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ CH ₂ ] ₂ Si (OCH ₃ ) ₂ , (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ And so on.

  Examples of zirconium alkoxides include zirconium ethoxide, zirconium isopropoxide, zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium 2-ethylhexyl oxide, zirconium 2-methyl-2-butoxide, tetrakis (trimethylsiloxy). ) Zirconium, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide bis (2,2,6,6, -tetramethyl-3,5-heptanedionate, zirconium dimethacrylate Dibutoxide, zirconium hexafluoropentanedionate, zirconium methacryloxyethyl acetoacetate tri-n-propoxide, zirconium 2,4 Pentanedionate, zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate, zirconium trifluoro pentanedionate, and the like.

  Examples of titanium alkoxides include titanium n-butoxide, titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium t-butoxide, titanium n-nonyl oxide, titanium i-butoxide, titanium methoxypropoxide. Side, Titanium Chlorotriisopropoxide, Titanium Dichloride Diethoxide, Titanium Iodoisopropoxide, Titanium Di n-Butoxide (Bis-2,4-Pentadionate), Titanium Di i-Propoxide (Bis-2,4-Pentadionate) Nate), titanium diisopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis (ethyl acetoacetate), titanium 2-ethylhexoxide, titanium oxide bis (pentadione) ), Titaniumoxybis (tetramethylheptanedionate), tetrakis (trimethylsiloxy) titanium, titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium methacrylate triisopropoxide, (2- Methacryloxyethoxy) triisopropoxy titanate, titanium methacryloxyethyl acetoacetate triisopropoxide, titanium methylphenoxide and the like.

  Examples of the aluminum alkoxide include aluminum (III) n-butoxide, aluminum (III) s-butoxide, aluminum (III) t-butoxide, aluminum (III) ethoxide, aluminum (III) isopropoxide, aluminum (III ) S-butoxide bis (ethyl acetoacetate), aluminum (III) di-s-butoxide ethyl acetoacetate, aluminum (III) diisopropoxide ethyl acetoacetate, aluminum (III) ethoxyethoxy ethoxide, aluminum hexafluoropenta Dionate, aluminum (III) 3-hydroxy-2-methyl-4-pyronate, aluminum (III) 9-octadecenyl acetoacetate diisopropoxide, aluminum (III) 2,4-pe Examples of tin alkoxides are tandionate, aluminum (III) phenoxide, aluminum (III) 2,2,6,6-tetramethyl-3,5-heptanedionate, tin (II) methoxide, tin (II) Etoxide, tetraisopropoxytin, tetra-t-butoxytin, tetra-n-butoxytin, bis (2,4-pentandionate) diclos, tin (II) 2,4-pentandionate, sodium tin ethoxide, etc. Can be mentioned.

  During the sol-gel reaction, the metal alkoxide is hydrolyzed and polycondensed in water and an organic solvent. At this time, it is preferable to use a catalyst. As a catalyst for hydrolysis, an acid is generally used. As the acid, an inorganic acid or an organic acid is used. Inorganic acids include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid, and organic acid compounds include carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, trifluoroacetic acid, perfluoro Octanoic acid, benzoic acid, phthalic acid, etc.), sulfonic acids (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acid (phosphoric acid dimethyl ester) , Phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyl titanic acid, aluminate, etc.), heteropolyacids (phosphomolybdic acid, phosphotungstic acid, etc.), and the like.

  The usage-amount of an acid is 0.0001-0.05 mol with respect to 1 mol of metal alkoxides, Preferably it is 0.001-0.01 mol.

  After hydrolysis, a basic compound such as an inorganic base or an amine may be added to bring the pH of the solution to near neutrality to promote condensation polymerization.

  Examples of inorganic bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia. Examples of organic base compounds include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, Dibutylamine, N, N-dimethylbenzylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.) Can be used.

  Other sol-gel catalysts can also be used in combination. Examples are given below.

For example, metal chelate compounds such as tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, (C ₄ H ₉ ) Carboxylic acid type organic tin compounds such as ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ and Sn (OCOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ Examples thereof include organic metal compounds such as organic tin compounds such as reaction products of organotin oxides such as SnO and ester compounds such as dimethyl ethyl silicate, diethyl maleate, and dioctyl phthalate. In addition, metal salts such as sodium naphthenate, potassium naphthenate, sodium octoate, sodium 2-ethylhexanoate, potassium laurate and the like are also preferably used.

  The proportion of the sol-gel catalyst compound in the composition is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, and more preferably 0.5 to 10% by mass with respect to the alkoxysilane that is the raw material of the sol liquid. % By mass.

  Next, the solvent used for the sol-gel reaction will be described. The solvent uniformly mixes each component in the sol solution, and at the same time prepares the solid content of the composition of the present invention, so that it can be applied to various coating methods to improve the dispersion stability and storage stability of the composition. Is. These solvents are not particularly limited as long as they can fulfill the above purpose. Preferable examples of these solvents include water and organic solvents that are highly miscible with water.

  Examples of organic solvents include tetrahydrofuran, dimethoxyethane, formic acid, acetic acid, methyl acetate, alcohols (methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, tert-butyl alcohol), ethylene glycol, diethylene glycol, triethylene glycol , Ethylene glycol monobutyl ether, acetone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and the like.

  For the purpose of adjusting the speed of the sol-gel reaction, an organic compound capable of multidentate coordination may be added to stabilize the metal alkoxide. Examples thereof include β-diketones and / or β-ketoesters such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, and alkanolamines.

  Next, a method for coating the gas barrier film of the present invention obtained by the sol-gel method will be described.

  The method for producing a gas barrier film in the present invention is formed using a wet method, and the sol solution can be applied by any of a spray method, a spin coat method, a roll coat method, a die coat method, a blade coat method, and a dip coat method. The law may be used. By these coating methods, a sol solution prepared from a metal alkoxide is coated on a resin film substrate and dried.

  The timing of hydrolysis may be any time during the production process. For example, a solution of the required composition is hydrolyzed and partially condensed to prepare the desired sol solution, and this is applied and dried, and a solution of the required composition is prepared and dried while subjecting it to hydrolysis and partial condensation. Method, application-After primary drying, a method of applying a water-containing liquid necessary for hydrolysis repeatedly and applying hydrolysis can be suitably employed.

  The drying temperature after coating is not particularly limited as long as it does not cause deformation of the resin film substrate as a support, but is preferably 150 ° C. or less, more preferably 30 to 150 ° C., and particularly preferably 50 to 130. ° C.

  In order to further increase the density of the coated and dried film and make it dense, energy treatment is performed as described above.

  These energy treatment temperatures can be employed without restriction between room temperature and the deformation temperature of the support, and are preferably 30 to 150 ° C, particularly preferably 50 to 130 ° C.

  In particular, when the temperature of the support is increased by energy treatment, the support may be kept in close contact with a backup roll or the like.

  In the present invention, the substance constituting the gas barrier film formed by the sol-gel method is SiOxCy (wherein the value of x is 1.5 to 2.0, preferably 1.7 to 2.0. And the value of y is 0 to 0.5, preferably in the range of 0 to 0.4.) And AlxOy (wherein the value of x is 1.05 to 2.0, preferably Is in the range of 1.7 to 2.0, and the value of y is preferably in the range of 1.0 to 3.0, preferably 2.0 to 3.0.

  Next, the resin film substrate used in the gas-barrier film of the present invention will be described.

  The resin film substrate is not particularly limited as long as it is a film formed of an organic material capable of holding the above-described gas barrier layer having a barrier property.

  Specifically, a homopolymer such as ethylene, polypropylene, butene or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, polyethylene terephthalate (PET), Polyester resins such as polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) Polyvinyl alcohol resins such as polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvini Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP) Fluorine-based resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA) can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a resin film base material.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film pure ace (manufactured by Teijin Ltd.), and cellulose triacetate film Konicakat Commercial products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  The resin film substrate is preferably transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. is there.

  In addition, the resin film substrate using the above-described resins or the like may be an unstretched film or a stretched film.

  The resin film substrate used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Moreover, in the resin film base material which concerns on this invention, you may perform surface treatments, such as a corona treatment, a flame treatment, a plasma treatment, a glow discharge process, a roughening process, a chemical treatment, before forming a vapor deposition film.

Further, an anchor coat agent layer may be formed on the surface of the resin film substrate according to the present invention for the purpose of improving the adhesion with the vapor deposition film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

  The resin film substrate is conveniently a long product wound up in a roll shape. Since the thickness of the base material varies depending on the use of the obtained gas barrier film, it cannot be specified unconditionally. However, when the gas barrier film is used as a packaging application, there is no particular limitation, and due to its suitability as a packaging material, 3 ˜400 μm, preferably 6-30 μm.

  Moreover, 10-200 micrometers is preferable as a film thickness of the film-shaped thing of the resin film base material used for this invention, More preferably, it is 50-100 micrometers.

The gas barrier film of the present invention has a water vapor transmission rate of 10 ⁻² g / m ² / day or less and an oxygen transmission rate of 10 ⁻² cc / m ² / day or less, such as an organic EL display or a high-definition color liquid crystal display. When used for applications requiring a high level of water vapor barrier property, the water vapor permeability measured according to JIS K7129 B method is preferably 0.001 g / m ² / day or less, and for organic EL display applications, Even if it is extremely small, a growing dark spot may be generated and the display life of the display may be extremely shortened. Therefore, the water vapor transmission rate may be less than 1 × 10 ⁻⁵ g / m ² / day. preferable.

  Next, the energy processing of the present invention will be described.

In the present invention, the light source used for the ultraviolet treatment is not limited, but a light source having a spectrum of 180 to 380 nm, such as a high pressure mercury lamp or a low pressure mercury lamp made of a quartz tube, can be used. The ultraviolet treatment is preferably performed after the gas barrier film is dried. As a method of ultraviolet irradiation, a high-pressure mercury lamp (generating a spectrum having a dominant wavelength of 365 nm) or a low-pressure mercury lamp (generating a spectrum having a dominant wavelength of 254 nm) Further, a KrF excimer laser (about 248 nm), an ArF excimer laser (about 193 nm) or the like can be used, and the irradiation light quantity is preferably 1 mJ / cm ^{2 to} 100 J / cm ² . If it exceeds 100 J / cm ² , the effect is saturated.

  As an electron beam used for electron beam processing, an electron beam generated from an electron beam tube is preferably used. There are two types of electron beam tubes, a field emission type and a thermionic emission type. In any system, an electron beam source including a cathode and an anode is provided in a chamber, and an object to be irradiated is disposed in the chamber.

  As a field emission type electron beam tube, for example, the one shown in FIG. 1 of JP-T-11-505670 is known. In a field emission type electron beam tube, the inside of a chamber in which an object to be irradiated is placed needs to have a high vacuum.

  Moreover, as a thermionic emission type electron beam tube, there is a vacuum tube type electron beam tube having a window (for example, refer to Japanese Patent Publication No. 10-512092). The electron beam tube includes a thermoelectron emitting unit and an electron beam accelerating unit in a vacuum vessel having a window through which an electron beam is transmitted, and accelerates thermoelectrons emitted from the thermoelectron emitting unit by the electron beam accelerating unit. And radiate from the window. If such an electron beam tube is used, an electron beam can be taken out into atmospheric pressure air from the window of the electron beam tube. Therefore, it is not necessary to reduce the atmosphere in which the irradiation object is disposed, and a vacuum pump and a vacuum chamber for reducing the pressure are not necessary, and the configuration of the electron beam irradiation processing apparatus is simple and easy to handle.

  For example, there are Ushio micro electron beam irradiation devices Min EB_labo STM-Chamber, Min-EB lab SCAN, etc., and these electron beam tubes can be used to irradiate an electron beam.

  High energy can be applied with high efficiency to a thin layer from the sample surface to several tens of μm by irradiation with electron beam irradiation. Various energy treatments can be performed by setting the acceleration voltage, current, and irradiation time of the electron beam.

As a result, it is possible to irradiate non-irradiated objects with an electron beam in a nitrogen-substituted atmosphere by placing an object on a transport table that moves in the horizontal direction. Can be set easily and accurately. The amount of electron beam irradiation is also preferably in the range of 1 mJ to 100 J / cm < ² >.

  The irradiation temperature of the electron beam is 0 ° C to 300 ° C, preferably room temperature to 250 ° C. If the irradiation temperature is less than room temperature, the effect is small. On the other hand, if the irradiation temperature becomes too high, not only the gas barrier film but also the resin film substrate is decomposed and the strength is lowered. Therefore, the upper limit of the irradiation temperature is preferably 250 ° C. Also at this time, when the support becomes too hot and is damaged, the support can be kept in close contact with a backup roll or the like.

  Microwaves can be generated by devices such as magnetrons and klystrons. As the microwave irradiation apparatus, for example, a microwave irradiation apparatus as shown in FIG. 1 can be used. A microwave generator having a frequency of 2.45 GHz is generally used due to restrictions of the microwave electron tube. For example, a microwave of 2.45 GHz is generated by a microwave generator (magnetron) 202 of 5 kW, and the waveguide 203 To the microwave oven 201 so that the film substrate F can be conveyed through the microwave oven, a microwave reflector and an absorption plate are installed at the entrance of the film, and a microwave agitator 207 is installed above the oven. Is installed. This microwave oven is, for example, a 6 m oven from the film inlet to the outlet, and an isolator, a power monitor and a matching unit are installed in the waveguide between the microwave generator and the oven, and the output detected by this power monitor. The output of the microwave generator can be adjusted according to the above.

  A microwave generator having a frequency of 2.45 GHz is generally used as the microwave, but a microwave having a frequency of 0.915 GHz can also be used.

The output is adjusted according to the type, composition, thickness, etc. of the sol-gel film that gives energy treatment. It is preferred that the irradiation dose of microwaves per area 1 cm ² is irradiated again so as to become a range of the irradiation light amount 1mJ~100J / cm ^2. For this, for example, irradiation is performed in the range of 0.1 seconds to several seconds using a microwave generation storage of about 0.01 to 10 W / cm ² .

  Next, corona discharge treatment, plasma discharge treatment, and flame plasma treatment, which are chemical energy treatments performed in addition to the ultraviolet ray treatment, electron beam treatment, or microwave treatment, will be described.

In the corona discharge treatment, a high voltage of alternating current or direct current is applied between the electrode and the roller to generate a corona discharge, and the film surface is processed by passing the film therethrough. Usually, the roller is placed on a metal roller. Hyperon rubber (rubber made of chlorosulfonated polyethylene), EPT rubber (ethylene / propylene / diene terpolymer, also called EPDM rubber), dielectric rubber such as silicon rubber and dielectric roller coated with ceramic are used. It is also possible to use a metal roller directly on the support without using a dielectric. The electric power to be applied varies depending on the thickness, composition, surface characteristics, etc. of the gas barrier film, and it is necessary to select conditions. However, the electric power in the range of 0.01 to 10 W / cm ² is used for 0.1 seconds to several seconds. Discharge treatment in the range.

  If the applied power is too high, problems such as damage to the film properties, wrinkles, and surface roughness may occur.

The plasma treatment includes atmospheric pressure plasma treatment and low pressure plasma treatment, and atmospheric pressure plasma treatment that is possible at atmospheric pressure is preferable. In the plasma treatment, air, nitrogen, helium, argon or the like is preferable as the atmospheric gas. Helium and argon gas are particularly preferable. The atmosphere gas may contain oxygen, methane, carbon dioxide, nitrogen (except in the case of a nitrogen atmosphere), and ammonia in an amount of 1 ppm to 30% (volume ratio). The atmospheric pressure is preferably 1 Pa to 1 MPa, and atmospheric pressure is preferable from the viewpoint of workability and the like. However, since the starting voltage increases, to suppress this, it is preferable to sandwich a dielectric on the discharge electrode surface, to use helium or argon as the atmospheric gas, and to use AC or high frequency as the power source. The frequency is preferably 1 kHz to 1 GHz. The power to be applied varies depending on the thickness, composition, surface characteristics, etc. of the gas barrier film, as in the case of the corona discharge treatment, and it is necessary to select conditions according to the required adhesion, but it is 0.01 to 10 W / cm ² . Discharge treatment is performed in the range of 0.1 seconds to several seconds using electric power in the range. If the applied power is too high, the surface smoothness may be impaired, and problems such as scattering of scattered substances due to discharge may occur.

  Flame plasma treatment (flame treatment) can be performed using, for example, a flame plasma treatment apparatus as shown in FIG. The treatment conditions were such that the contact time between the flame and the film was about 0.1 seconds, the ratio of the contact area of the outer flame to the maximum area of the inner flame was 5, and the distance from the tip of the inner flame I was 5 mm. The maximum area of the internal flame is a value obtained by multiplying the width of the center of the internal flame I in FIG. 2 by the processing width of the film, and the contact area of the external flame E is the effective flame G (also external flame). It is a value obtained by multiplying the width in contact with the film to be processed and the processing width of the film. The processing may be performed in the range of 0.1 second to several seconds.

  The gas barrier film of the present invention formed on the resin film base material is subjected to these two kinds of different energy treatments in sequence, so that it becomes a dense and dense film, and the gas barrier property of the gas barrier film is improved.

  Next, the gas barrier film according to the present invention having the energy-treated gas barrier film will be described.

  FIG. 3 is a schematic view showing the configuration of the transparent gas barrier film of the present invention.

  The gas barrier film 1 has a gas barrier film 3 formed by a single layer of the method of the present invention on a resin film substrate Y, for example, polyethylene terephthalate. Further, the gas barrier film of the present invention may be formed by laminating two or more gas barrier films, and the gas barrier film 2 includes a resin film substrate Y, at least two layers of gas barrier films 3, and two gas barrier films. It has the stress relaxation layer 4 containing the polymer whose elastic modulus is lower than the gas barrier film located. Since the ceramic film according to the present invention has a dense structure and high hardness, when laminating, it is preferable to divide such a stress relaxation layer into a plurality of layers. The stress relaxation layer has a function of relieving stress generated in, for example, a metal oxide film that is a gas barrier film and preventing generation of cracks and defects in the gas barrier film.

  Next, the polymer layer used here will be described.

  The polymer layer according to the present invention is a thin film mainly composed of an inorganic polymer, an organic polymer, an organic-inorganic hybrid polymer, etc., and the film thickness is approximately 5 to 500 nm, and the relative hardness with respect to the gas barrier layer described above. A low layer with an average carbon content of 5% or more in the layer, also called a stress relaxation layer.

  The inorganic polymer applicable in the present invention is a film having an inorganic skeleton as a main structure and containing an organic component, and includes a polymer obtained by polymerizing an organometallic compound.

  These inorganic polymers are not particularly limited, and for example, silicon compounds such as silicone and polysilazane, titanium compounds, aluminum compounds, boron compounds, phosphorus compounds, and tin compounds can be used.

  The silicon compound that can be used in the present invention is not particularly limited, but is preferably tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltrimethyl. Ethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldi Vinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoro Propyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane , Aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimethoxyvinylsilane , Trimethyl-3-vinylthiopropylsilane, phenyltrimethylsilane Dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyl Trimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryl Loxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dibu Toxidimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, di Acetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane , Octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethyl Nylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyldi Siloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotri Siloxane, octamethylcyclotetrasiloxane, 1, 3, 5 7-tetraethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may this include decamethylcyclopentasiloxane, and the like.

  As the organic polymer, known polymerizable organic compounds can be used, and among them, a polymerizable ethylenically unsaturated bond-containing compound having an ethylenically unsaturated bond in the molecule is preferable. Radically polymerizable monomers, polyfunctional monomers and polyfunctional oligomers having a plurality of addition-polymerizable ethylenic double bonds in a molecule generally used for resins curable by light, heat, ultraviolet rays, etc. be able to.

  These polymerizable ethylenic double bond-containing compounds are not particularly limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxy. Monofunctional acrylic acid esters such as ethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or Methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate. Tel, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate neo Diacrylate of pentyl glycol, diacrylate of neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl- 5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylo Difunctional acrylic acid esters such as ε-caprolactone adduct of diacrylate, diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itacon in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acids, crotonic acid, maleic esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, ε-cap of dipentaerythritol hexaacrylate Lactone adducts, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate and other polyfunctional acrylic acid esters, or these acrylates Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of methacrylate, itaconate, crotonate, and maleate.

  Prepolymers can also be used as described above. A prepolymer may use together 1 type (s) or 2 or more types, and may mix and use the above-mentioned monomer and / or oligomer.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  In addition, the organic polymer applicable to the polymer layer according to the present invention can be easily formed by using an organic substance capable of plasma polymerization as the thin film forming gas. Examples of the plasma-polymerizable organic substance include hydrocarbons, vinyl compounds, halogen-containing compounds, and nitrogen-containing compounds.

  Examples of the hydrocarbon include ethane, ethylene, methane, acetylene, cyclohexane, benzene, xylene, phenylacetylene, naphthalene, propylene, camphor, menthol, toluene, isobutylene, and the like.

  Examples of the vinyl compound include acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, allyl methacrylate, acrylamide, styrene, α-methyl styrene, vinyl pyridine, vinyl acetate, vinyl methyl ether, and the like.

  Examples of halogen-containing compounds include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl methacrylate.

  Examples of the nitrogen-containing compound include pyridine, allylamine, butylamine, acrylonitrile, acetonitrile, benzonitrile, methacrylonitrile, aminobenzene and the like.

  Examples of the organic-inorganic hybrid polymer according to the present invention include a film in which an inorganic (organic) substance is dispersed in an organic (inorganic) polymer, and a film having both an inorganic skeleton and an organic skeleton as a main structure. The organic-inorganic hybrid polymer that can be applied to the present invention is not particularly limited, but it is preferable to use an appropriate combination of the above-described inorganic polymer and organic polymer.

  These gas barrier films according to the present invention can be used as various sealing materials and films.

  These gas barrier films of the present invention can also be used for display elements such as organic EL elements. When used in an organic EL device, the gas barrier film of the present invention is transparent. Therefore, the gas barrier film can be used as a base material and light can be extracted from this side. That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin substrate for an organic electroluminescence element. Then, using the ITO transparent conductive film provided on the substrate as an anode, an organic EL material layer including a light emitting layer is provided thereon, and a cathode made of a metal film is further formed to form an organic EL element. The organic EL element layer can be sealed by stacking another sealing material (although it may be the same) and adhering the gas barrier film substrate to the surroundings and encapsulating the element. The influence of the gas on the device can be sealed.

  The organic electroluminescent resin substrate according to the present invention is obtained by forming a transparent conductive thin film on the gas barrier film of the gas barrier film. The transparent conductive thin film is a transparent conductive film that becomes an anode when an organic EL element is formed.

The transparent conductive film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin, and has a specific resistance of 10 ⁻⁴ Ω. An ITO film having excellent conductivity on the order of cm can be obtained, but it is preferably formed by an atmospheric pressure plasma CVD method.

  In the atmospheric pressure plasma CVD method, the gas used for forming the transparent conductive film varies depending on the type of the transparent conductive film provided on the substrate, but basically, an inert gas and a transparent conductive film are formed. It is a mixed gas of reactive gas that becomes a plasma state. Here, the inert gas is a group 18 element of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, nitrogen gas, and the like, but argon or helium is particularly preferable. Used. A plurality of reactive gases can be used in the present invention, but at least one kind contains a component that is in a plasma state in the discharge space and forms a transparent conductive film. Although there is no restriction | limiting in particular as such reactive gas, An organometallic compound is used preferably. The type of the organometallic compound is not limited, but an organometallic compound having oxygen in the molecule is preferable, and in particular, an organometallic compound such as β-diketone metal complex, metal alkoxide, or alkyl metal is preferably used. Among the raw material compounds used for forming the transparent conductive thin film, preferred examples include indium hexafluoropentanedionate, indiummethyl (trimethyl) acetylacetate, indium acetylacetonate, indium isoporopoxide, indium trifluoropentanedionate. , Tris (2,2,6,6-tetramethyl 3,5-heptanedionate) indium, di-n-butylbis (2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di- Examples thereof include t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, zinc acetylacetonate and the like.

  Of these, indium acetylacetonate, tris (2,2,6,6-tetramethyl 3,5-heptanedionate) indium, zinc acetylacetonate and di-n-butyldiacetoxytin are particularly preferable. . These organometallic compounds are generally commercially available. For example, indium acetylacetonate can be easily obtained from Tokyo Chemical Industry Co., Ltd.

  In forming the conductive film, in addition to the organometallic compound containing at least one oxygen atom in the molecule, a doping gas used for improving the conductivity can be used. Examples of the reactive gas used for doping include aluminum isopropoxide, nickel acetylacetonate, manganese acetylacetonate, boron isopropoxide, n-butoxyantimony, tri-n-butylantimony, di-n-butylbis ( 2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, tetrabutyltin, zinc acetylacetonate, propylene hexafluoride, A cyclobutane octafluoride, methane tetrafluoride, etc. can be mentioned.

  Further, by using water as a reaction gas in addition to the reaction gas containing the constituent elements of the transparent conductive film, it is possible to produce a transparent conductive film having high conductivity and a high etching rate. The amount of water mixed in the reaction gas is preferably in the range of 0.0001 to 10% in the mixed gas of the reactive gas and the inert gas. More preferably, it is in the range of 0.001 to 1%.

  Reactive gases include organometallic compounds containing elements that constitute transparent conductive films and water, oxidizing gases such as oxygen, reducing gases such as hydrogen, etc., nitrogen monoxide, nitrogen dioxide, carbon monoxide Carbon dioxide or the like can be used as appropriate.

The amount ratio of the reactive gas used as the main component of the transparent conductive film and the reactive gas used in a small amount for the purpose of doping differs depending on the type of the transparent conductive film to be formed. For example, in an ITO film obtained by doping tin with indium oxide, the reactive gas amount is adjusted so that the In: Sn atomic number ratio of the obtained ITO film is in the range of 100: 0.1 to 100: 15. To do. Preferably, it adjusts so that it may become the range of 100: 0.5-100: 10. The atomic ratio of In: Sn can be determined by XPS measurement. In a transparent conductive film (referred to as an FTO film) obtained by doping fluorine into tin oxide, the reaction is performed so that the Sn: F atomic ratio of the obtained FTO film is in the range of 100: 0.01 to 100: 50. Adjust the quantity ratio of sex gases. The atomic ratio of Sn: F can be determined by XPS measurement. In the In ₂ O ₃ —ZnO amorphous transparent conductive film, the amount ratio of the reactive gas is adjusted so that the In: Zn atomic ratio is in the range of 100: 50 to 100: 5. The atomic ratio of In: Zn can be determined by XPS measurement.

  Furthermore, the reactive gas includes a reactive gas that is a main component of the transparent conductive film and a reactive gas that is used in a small amount for the purpose of doping. Further, in the present invention, silicon is introduced in addition to the main metal element constituting the transparent conductive film and the metal element to be doped. Although there is no restriction | limiting in the introduction method of silicon, when forming a transparent conductive film, it is also possible to add reactive gas as a reactive gas in order to adjust the resistance value of a transparent conductive film. As the reactive gas used for adjusting the resistance value of the transparent conductive film, an organometallic compound, particularly an organometallic compound such as a β-diketone metal complex, a metal alkoxide, or an alkyl metal is preferably used. Specifically, the following can be mentioned. Examples of silicon compounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, and methyltrimethoxy. Silane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane And hexyltrimethoxysilane. Among these, tetraethoxysilane is preferable in terms of stability and vapor pressure.

  As the film thickness of the transparent conductive film, a transparent conductive film in the range of 0.1 nm to 1000 nm is preferable.

  Next, the atmospheric pressure plasma CVD method that can be suitably used for forming the transparent conductive thin film will be described in more detail.

  In the plasma CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where the gas in the plasma state exists, and the volatilized and sublimated organometallic compound is introduced into the plasma space and decomposed. By spraying on the substrate after the reaction has occurred, an inorganic thin film is formed. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the substrate on which the inorganic material is formed and can sufficiently form the film on the resin film substrate.

  Especially in the plasma CVD method near atmospheric pressure, it is not necessary to reduce the pressure and the productivity is high, and since the plasma density is high, the film forming speed is high, and compared with the normal conditions of the CVD method. Under a high pressure condition under atmospheric pressure, the mean free path of gas is very short, so that a very flat film can be obtained, and such a flat film has good optical characteristics.

  First, an example of a plasma film forming apparatus used in the present invention will be described with reference to FIGS. In the figure, symbol F is a long film as an example of a substrate.

  In the plasma discharge processing apparatus described in FIG. 4 or FIG. 5 and the like, the source gas containing the metal and the decomposition gas are appropriately selected from the gas supply means, and these reactive gases are mainly in a plasma state. The ceramic film can be obtained by mixing discharge gas that tends to be mixed and feeding the gas to a plasma discharge generator.

  As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as described above. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  FIG. 4 shows a jet-type atmospheric pressure plasma discharge processing apparatus. In addition to the plasma discharge processing apparatus and electric field applying means having two power sources, FIG. 4 is not shown (shown in FIG. 5 described later). Is an apparatus having gas supply means and electrode temperature adjustment means.

The plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the frequency ω ₁ from the first power source 21 is connected to the first electrode 11 between the counter electrodes. A first high-frequency electric field of electric field strength V ₁ and current I ₁ is applied, and a second high-frequency electric field of frequency ω ₂ , electric field strength V ₂ and current I ₂ from the second power source 22 is applied to the second electrode 12. Is applied. The first power source 21 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power source 22, and the first frequency ω ₁ of the first power source 21 is higher than the second frequency ω ₂ of the second power source 22. A low frequency can be applied.

  A first filter 23 is installed between the first electrode 11 and the first power source 21 to facilitate passage of current from the first power source 21 to the first electrode 11, and current from the second power source 22. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.

  In addition, a second filter 24 is installed between the second electrode 12 and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode, and from the first power source 21. It is designed to ground the current and make it difficult to pass the current from the first power source 21 to the second power source.

  A gas G is introduced from a gas supply means as shown in FIG. 5 to be described later into the space (discharge space) 13 between the opposing electrodes of the first electrode 11 and the second electrode 12, and the first electrode 11 and the second electrode A processing space created between the lower surface of the counter electrode and the base material F by generating a discharge by applying a high-frequency electric field from 12 and blowing the gas G in a plasma state to the lower side of the counter electrode (the lower side of the paper). Is filled with plasma gas G ° and unwound from a base roll (unwinder) (not shown) to be transported, or processed onto the base material F transported from the previous process. A thin film is formed near position 14. During the thin film formation, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the base material during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the base material in the width direction or the longitudinal direction does not occur as much as possible.

  Since a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses can be connected in series and discharged in the same plasma state at the same time, it can be processed many times and processed at high speed. In addition, if each apparatus jets gas in a different plasma state, a laminated thin film having different layers can be formed.

  FIG. 5 is a schematic view showing an example of an atmospheric pressure plasma discharge processing apparatus of a system for processing a substrate between counter electrodes useful for the present invention.

  The atmospheric pressure plasma discharge processing apparatus according to the present invention is an apparatus having at least a plasma discharge processing apparatus 30, an electric field applying means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjusting means 60.

  FIG. 5 shows a thin film formed by subjecting the substrate F to plasma discharge treatment between the opposing electrodes (discharge space) 32 between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36. To do.

In the discharge space (between the counter electrodes) 32 between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36, the roll rotating electrode (first electrode) 35 has a first power source. The first high-frequency electric field having frequency ω ₁ , electric field strength V ₁ and current I ₁ from 41, and the frequency ω ₂ and electric field strength V ₂ from the second power source 42 to the square tube fixed electrode group (second electrode) 36. A second high-frequency electric field of current I ₂ is applied.

  A first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes a current from the first power supply 41 to the first electrode. The current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass. Further, a second filter 44 is provided between the square tube type fixed electrode group (second electrode) 36 and the second power source 42, and the second filter 44 is connected from the second power source 42 to the second electrode. It is designed so that the current from the first power supply 41 is grounded and the current from the first power supply 41 to the second power supply is difficult to pass.

In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped fixed electrode group 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power supply preferably applies a higher frequency electric field strength (V ₁ > V ₂ ) than the second power supply. Further, the frequency has the ability to satisfy ω ₁ <ω ₂ .

The current is preferably I ₁ <I ₂ . Current I ₁ of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . The current I ₂ of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge processing vessel 31 from the air supply port 52 while controlling the flow rate.

  The base material F is unwound from the original winding (not shown) and is transported or is transported from the previous process, and the air and the like that is entrained by the base material by the nip roll 65 through the guide roll 64 is blocked. Then, while being wound while being in contact with the roll rotating electrode 35, it is transferred between the square tube fixed electrode group 36 and the roll rotating electrode (first electrode) 35 and the square tube fixed electrode group (second electrode) 36. An electric field is applied from both of them to generate discharge plasma between the counter electrodes (discharge space) 32. The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35. The base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.

  Discharged treated exhaust gas G ′ is discharged from the exhaust port 53.

  In order to heat or cool the roll rotating electrode (first electrode) 35 and the rectangular tube type fixed electrode group (second electrode) 36 during the formation of the thin film, a medium whose temperature is adjusted by the electrode temperature adjusting means 60 is used as a liquid feed pump. P is sent to both electrodes through the pipe 61, and the temperature is adjusted from the inside of the electrode. Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.

  FIG. 6 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 5 and the dielectric material coated thereon.

  In FIG. 6, a roll electrode 35a is formed by covering a conductive metallic base material 35A and a dielectric 35B thereon. In order to control the electrode surface temperature during the plasma discharge treatment, a temperature adjusting medium (water, silicon oil or the like) can be circulated.

  FIG. 7 is a perspective view showing an example of the structure of the conductive metallic base material of the rectangular tube electrode and the dielectric material coated thereon.

  In FIG. 7, a rectangular tube electrode 36a has a coating of a dielectric 36B similar to FIG. 6 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.

  In addition, the number of the rectangular tube-shaped fixed electrodes is set in plural along the circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is a full square tube type facing the roll rotating electrode 35. It is represented by the sum of the area of the fixed electrode surface.

  The rectangular tube electrode 36a shown in FIG. 7 may be a cylindrical electrode. However, the rectangular tube electrode is preferably used in the present invention because it has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode. .

  6 and 7, a roll electrode 35a and a rectangular tube electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then sealing the inorganic compound. Is subjected to a sealing treatment. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metal base materials 35A and 36A include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum, and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.

  When the dielectric is provided on one of the electrodes, the distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metal base material of the other electrode. Say that. When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of carrying out, 0.1 to 20 mm is preferable, and 0.2 to 2 mm is particularly preferable.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but can be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation. In FIG. 4, it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with an object made of the above material.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic spray coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic sprayed coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or a titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2004-68143, 2003-49272, International Patent No. 02/48428, etc. in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.

  In the case of a transparent conductive film, it is possible to adjust the characteristics of the transparent conductive film by applying heat after being formed under a pressure near atmospheric pressure. This heat treatment can also change the amount of hydrogen in the film. The heat treatment temperature is preferably in the range of 50 to 300 ° C. Preferably it is the range of 100-200 degreeC. The atmosphere for heating is not particularly limited. It can be appropriately selected from an air atmosphere, a reducing atmosphere containing a reducing gas such as hydrogen, an oxidizing atmosphere containing an oxidizing gas such as oxygen, or a vacuum or an inert gas atmosphere. When taking a reducing or oxidizing atmosphere, it is preferable to use a reducing gas or oxidizing gas diluted with an inert gas such as a rare gas or nitrogen. In such a case, the concentration of the reducing gas and the oxidizing gas is preferably 0.01 to 5%, more preferably 0.1 to 3%.

  Moreover, since the transparent conductive film obtained by the method for forming a transparent conductive film of the present invention uses an organometallic compound as a reactive gas, it may contain a trace amount of carbon. In that case, the carbon content is preferably 0 to 5.0 atom concentration. Particularly preferably, it is within the range of 0.01 to 3 atomic number concentration.

  In the present invention, the ceramic film and the transparent conductive film are formed under a pressure in the vicinity of atmospheric pressure, but the temperature of the substrate at that time is not particularly limited. When glass is used as the substrate, it is preferably 300 ° C. or lower, and when polymer is used, 200 ° C. or lower is preferable.

  Next, an organic electroluminescence device using the gas barrier film and a resin substrate for an organic electroluminescence device having a transparent conductive film formed thereon will be described.

  One feature of the organic EL device according to the present invention is that a gas barrier film having the ceramic film is used as a substrate.

  In the gas barrier film having the ceramic film, a transparent conductive thin film is further formed on the ceramic film, and an organic electroluminescence (EL) material film constituting the organic EL element is formed thereon, and a metal serving as a cathode. It laminates | stacks with a layer, and also seals it on another by using another gas barrier film as a sealing film, and carrying out an overlap adhesion.

  As another sealing material (sealing film) used, a gas barrier film having a gas barrier film having the dense structure according to the present invention can be used. Moreover, it is not limited to what was formed by the sol-gel method. For example, it may be formed by slow deposition, plasma CVD, or the like as long as it has a dense structure having gas barrier properties. Also, known gas barrier films used for packaging materials, such as plastic films deposited with silicon oxide or aluminum oxide, dense ceramic layers and flexible impact relaxation polymer layers are alternately laminated. A gas barrier film or the like having a configuration can be used as the sealing film. In particular, a resin-laminated (polymer film) metal foil cannot be used as a gas barrier film on the light extraction side, but it is a low-cost and further low moisture-permeable sealing material and does not intend to extract light (with transparency). When not required), it is preferable as a sealing film.

  In the present invention, the metal foil refers to a metal foil or film formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. .

  As metal foil, there is no limitation in particular in the kind of metal, for example, copper (Cu) foil, aluminum (Al) foil, gold (Au) foil, brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy Examples thereof include foil, stainless steel foil, tin (Sn) foil, and high nickel alloy foil. Among these various metal foils, a particularly preferred metal foil is an Al foil.

  The thickness of the metal foil is preferably 6 to 50 μm. If it is less than 6 μm, depending on the material used for the metal foil, pinholes may be vacant during use, and required barrier properties (moisture permeability, oxygen permeability) may not be obtained. If it exceeds 50 μm, the cost may increase depending on the material used for the metal foil, and the merit of the film may be reduced because the organic EL element becomes thick.

  As a resin film in a metal foil laminated with a resin film (polymer film), various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene resin , Polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon resin, vinylidene chloride Based resins and the like. Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. In addition, a polyethylene resin having a low density or a high density can be used.

  Among the above polymer materials, nylon (Ny), nylon (KNy) coated with vinylidene chloride (PVDC), unstretched polypropylene (CPP), stretched polypropylene (OPP), polypropylene coated with PVDC (KOP), polyethylene Use terephthalate (PET), cellophane coated with PVDC (KPT), polyethylene-vinyl alcohol copolymer (Eval), low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) Is preferred. As these thermoplastic films, a multilayer film formed by coextrusion with a different film, a multilayer film laminated by changing the stretching angle, and the like can be used as needed. Furthermore, it is naturally possible to combine the density and molecular weight distribution of the film used to obtain the required physical properties of the packaging material.

  The thickness of the polymer film cannot be generally defined, but is preferably 3 to 400 μm, more preferably 10 to 200 μm, and further preferably 10 to 50 μm.

  As a method of coating (laminating) a polymer film on one side of a metal foil, a generally used laminating machine can be used. As the adhesive, polyurethane-based, polyester-based, epoxy-based, acrylic-based adhesives and the like can be used. You may use a hardening | curing agent together as needed. A dry lamination method, a hot melt lamination method and an extrusion lamination method can also be used, but the dry lamination method is preferred.

  Films in which one side of a metal foil is coated with a polymer film are commercially available for packaging materials. For example, a dry laminate film having a configuration of adhesive layer / aluminum film 9 μm / polyethylene terephthalate (PET) 38 μm (a two-component reaction type urethane adhesive with an adhesive layer thickness of 1.5 μm) is available. It is possible to seal the cathode side of the organic EL element.

  Moreover, as a film for sealing, it is preferable to use a ceramic film formed on a metal foil opposite to the polymer film in a film in which one side of the metal foil is coated with a polymer film. As the ceramic film, the ceramic film according to the present invention may be formed by vapor deposition, plasma CVD, or the like as described above, and the manufacturing method is not limited. The film thickness is in the range of 1 to 2000 nm.

  As will be described later, as a method for sealing an organic EL element formed with the gas barrier film according to the present invention as a substrate, using another gas barrier film, for example, a commonly used impulse sealer heat fusion property The method of laminating the resin layer, fusing with an impulse sealer, and sealing is preferable. In this case, the gas barrier films are sealed with each other when the film thickness exceeds 300 μm. The film thickness is desirably 300 μm or less because the heat resistance by an impulse sealer or the like becomes difficult due to the deterioration of the properties.

[Encapsulation of organic EL elements]
In this invention, after forming a transparent conductive film on the resin film (gas barrier film) which has the said gas barrier film concerning this invention, and forming each layer of organic EL element material on the produced resin base material for organic electroluminescence The organic electroluminescence device can be sealed using the sealing film so as to cover the cathode surface with the sealing film in an environment purged with an inert gas.

As the inert gas, a rare gas such as He or Ar is preferably used in addition to N ₂ , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90 to 99.99. It is preferably 9% by volume. Preservability is improved by sealing in an environment purged with an inert gas.

  Moreover, when sealing an organic EL element using the metal foil on which the resin film (polymer film) is laminated, the laminated resin film surface is opposed to the cathode surface of the organic EL element and sealed. Can do.

  As a sealing method for bonding the sealing film to the cathode of the organic EL element, as described above, a resin film that can be fused with an impulse sealer that is generally used, for example, ethylene vinyl acetate copolymer (EVA) or polypropylene (PP) film There is a method in which a heat-fusible film such as a polyethylene (PE) film is laminated, and is fused and sealed with an impulse sealer.

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 to 2.5 μm. However, when the coating amount of the adhesive is too large, tunneling, oozing, crimping, etc. may occur, so the amount of the adhesive is preferably adjusted to 3 to 5 μm in dry film thickness. It is preferable.

  Hot melt lamination is a method in which a hot melt adhesive is melted and an adhesive layer is applied to a substrate, and the thickness of the adhesive layer is generally set within a wide range of 1 to 50 μm. Commonly used base resins for hot melt adhesives include EVA, EEA, polyethylene, butyl rubber, etc., rosin, xylene resin, terpene resin, styrene resin, etc. as tackifiers, wax etc. It is added as an agent.

  The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a substrate with a die, and the thickness of the resin layer can be generally set in a wide range of 10 to 50 μm.

  In general, LDPE, EVA, PP or the like is used as the resin used for the extrusion laminate.

  However, instead of sealing the laminated resin film surface facing the cathode surface of the organic EL element, a sealing film in which a ceramic film such as a silicon oxide film is formed on the metal foil of the sealing film is used. The ceramic film surface is preferably bonded to the cathode of the organic EL element. When the polymer film surface of the sealing film is bonded to the cathode of the organic EL element, conduction may be partially generated, or electrical decoration associated therewith may be generated, thereby generating a dark spot.

  FIG. 8 is a schematic cross-sectional view of an organic EL element sealed by bonding the resin barrier aluminum foil with a silicon oxide film and the gas barrier film after each layer of the organic EL element is formed on the gas barrier film of the present invention. Indicates.

  In FIG. 8, on a gas barrier film having a ceramic film 3 according to the present invention formed on a resin film substrate Y, an anode (ITO) 4, an organic EL layer 5 including a light emitting layer, a cathode (for example, Aluminum) 6 is formed to form an organic EL element. Furthermore, another sealing film S is stacked on the cathode, and the organic EL element including the organic EL material layer is sealed by adhering the periphery of the base film. In the sealing film S, the ceramic film 3 according to the present invention is formed on a metal (aluminum) foil 7, and a resin layer 8 is laminated on the opposite side of the metal foil, and the ceramic film 3 side. Is bonded to the cathode. The arrow indicates the light extraction direction. In the figure, 9 is an adhesive.

  In forming such a sealing structure, a water-absorbing substance may be disposed in the sealing space in the sealing structure, or a layer that absorbs water vapor such as a water absorption layer may be provided in the structure. Good.

  Next, the organic EL material layer (constituent layer) constituting the organic EL element will be described.

  In addition, although details of the organic EL material layer will be described later, in the present invention, an element having a phosphorescent type light emitting layer containing a phosphorescent dopant in the light emitting layer is preferable because of high luminous efficiency.

[Organic EL device]
Next, the constituent layers of the organic EL element according to the present invention will be described in detail. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(1) Anode / light emitting layer / electron transport layer / cathode (2) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (4) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (5) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (anode)
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(cathode)
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the said metal with a film thickness of 1-20 nm on a cathode, a transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

  Next, an injection layer, a blocking layer, an electron transport layer, and the like used as a constituent layer of the organic EL element of the present invention will be described.

(Injection layer: electron injection layer, hole injection layer)
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

(Blocking layer: hole blocking layer, electron blocking layer)
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.

(Light emitting layer)
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The light emitting layer of the organic EL device of the present invention preferably contains the following host compound and dopant compound. Thereby, the luminous efficiency can be further increased.

  The light-emitting dopant is roughly classified into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

  Representative examples of the former (fluorescent dopant) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, Examples include perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Typical examples of the latter (phosphorescent dopant) are preferably complex compounds containing metals of Group 8, Group 9, and Group 10 in the periodic table of elements, and more preferably iridium compounds and osmium compounds. Of these, iridium compounds are most preferred. Specifically, it is a compound described in the following patent publications.

  International Publication No. 00/70655 pamphlet, Japanese Patent Laid-Open No. 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859. Gazette, 2002-299060, 2001-313178, 2002-302671, 2001-345183, 2002-324679, WO 02/15645, JP-A-2002 No. 332291, No. 2002-50484, No. 2002-332292, No. 2002-83684, No. 2002-540572, No. 2002-117978, No. 2002-338588, 002-170684, 2002-352960, WO 01/93642 pamphlet, JP 2002-50483, 2002-100476, 2002-173684, 2002-359082 No. 2002-175844, No. 2002-363552, No. 2002-184582, No. 2003-7469, No. 2002-525808, No. 2003-7471, No. 2002-525833. Publication No. 2003-31366 Publication No. 2002-226495 Publication No. 2002-234894 Publication No. 2002-2335076 Publication No. 2002-241751 Publication No. 2001-319779 Publication No. 2001-3197 0, JP same 2002-62824, JP same 2002-100474, JP same 2002-203679, JP same 2002-343572, JP same 2002-203678 Patent Publication.

  Some examples are shown below.

  The light emitting dopant may be used by mixing a plurality of kinds of compounds.

<Light emitting host>
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more compounds. For other compounds, “dopant compound ( Simply referred to as a dopant). " For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if a light emitting layer is comprised from 3 types of compound A, compound B, and compound C, and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, Compound C is a host compound.

  The light-emitting host used in the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligo Those having a basic skeleton such as an arylene compound, or a carboline derivative or diazacarbazole derivative (herein, a diazacarbazole derivative is a nitrogen atom in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is a nitrogen atom) And the like.) And the like.

  Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

  Specific examples of carboline derivatives, diazacarbazole derivatives and the like are given below, but the present invention is not limited thereto.

  The light emitting host used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

As the light-emitting host, a compound having a hole transporting ability and an electron transporting ability and preventing a long wavelength of light emission and having a high Tg (glass transition temperature) is preferable.
As specific examples of the light-emitting host, compounds described in the following documents are suitable. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Further, a plurality of known host compounds may be used in combination. Moreover, it becomes possible to mix different light emission by using multiple types of dopant compounds, and can thereby obtain arbitrary luminescent colors. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  The color emitted by the organic EL element of the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured by Minolta Sensing Co., Ltd. is applied to the CIE chromaticity coordinates.

  The light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. This light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are composed of one or more kinds, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and similarly to the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC can be used. A semiconductor can also be used as an electron transport material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Examples of the resin film constituting the gas barrier film that can be used in the organic EL device according to the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, Cellulose esters such as cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate (TAC), cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotact Tick polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide Polyethersulfone (PES), polysulfones, polyetherketoneimide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) And the like.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

(Method for producing organic EL element)
A method for manufacturing the organic EL element will be described in detail below.
As an example of the organic EL element, a method for producing an organic EL element composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is deposited on the substrate (the gas barrier film of the present invention) so as to have a thickness of 1 μm or less, preferably 10 to 200 nm. Thus, an anode is produced. Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are organic EL element materials, is formed thereon.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁻⁶ to 10 ⁻² Pa, a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature −50 to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 to 200 nm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained. The organic EL element is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The display device using the organic EL element of the present invention can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and the display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in a car. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  The lighting device using the organic EL element of the present invention includes home lighting, interior lighting, backlights for clocks and liquid crystals, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, and optical communication processors. Examples include, but are not limited to, a light source and a light source of an optical sensor.

  Moreover, you may use as an organic EL element which gave the organic EL element of this invention the resonator structure. Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.

  A gas barrier film in which a ceramic film having a residual stress in a predetermined range is coated on a resin film having a high gas barrier property according to the present invention does not require a multilayer ceramic film as a gas barrier layer, and is excellent in productivity. In addition, it is a highly productive gas barrier film that can be easily processed so as to have a concavo-convex shape for diffracting or diffusing light for improving light extraction from the light emitting layer on the surface.

[Display device]
The organic EL element of the present invention may be used as one kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using three or more organic EL elements of the present invention having different emission colors. Alternatively, it is possible to make a single color emission color, for example, white emission, into BGR using a color filter to achieve full color. Further, it is possible to convert the emission color of the organic EL to another color by using a color conversion filter, and in this case, λmax of the organic EL emission is preferably 480 nm or less.

  An example of a display device composed of the organic EL element of the present invention will be described with reference to the drawings.

  FIG. 9 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  The display 101 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. The pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display image information on the display unit A.

  FIG. 10 is a schematic diagram of the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 106, a plurality of pixels 103, and the like on a substrate. The main members of the display unit A will be described below. FIG. 9 shows a case where light emitted from the pixel 103 is extracted in the direction of the white arrow (downward).

  The scanning lines 105 and the plurality of data lines 106 in the wiring portion are each made of a conductive material, and the scanning lines 105 and the data lines 106 are orthogonal to each other in a grid pattern and are connected to the pixels 103 at orthogonal positions (details are shown in FIG. Not shown).

  When a scanning signal is applied from the scanning line 105, the pixel 103 receives an image data signal from the data line 106 and emits light according to the received image data. Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 11 is a schematic diagram of a pixel.

  The pixel includes an organic EL element 110, a switching transistor 111, a driving transistor 112, a capacitor 113, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 110 for a plurality of pixels and arranging them on the same substrate.

  In FIG. 11, an image data signal is applied from the control unit B to the drain of the switching transistor 111 via the data line 106. When the scanning signal is applied from the control unit B to the gate of the switching transistor 111 via the scanning line 105, the driving of the switching transistor 111 is turned on, and the image data signal applied to the drain is supplied to the capacitor 113 and the driving transistor 112. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 113 is charged according to the potential of the image data signal, and the drive transistor 12 is turned on. The drive transistor 112 has a drain connected to the power supply line 107 and a source connected to the electrode of the organic EL element 110, and the power supply line 107 connects to the organic EL element 110 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 105 by the sequential scanning of the control unit B, the driving of the switching transistor 111 is turned off. However, even if the driving of the switching transistor 111 is turned off, the capacitor 113 maintains the potential of the charged image data signal, so that the driving of the driving transistor 112 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 110 continues. When a scanning signal is next applied by sequential scanning, the driving transistor 112 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 110 emits light.

  That is, the organic EL element 110 emits light by the switching transistor 111 and the driving transistor 112 that are active elements for the organic EL elements 110 of each of the plurality of pixels, and the light emission of the organic EL elements 110 of the plurality of pixels 103. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 110 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.

  The potential of the capacitor 113 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 12 is a schematic diagram of a passive matrix display device. In FIG. 14, a plurality of scanning lines 105 and a plurality of image data lines 106 are provided in a lattice shape so as to face each other with the pixel 103 interposed therebetween.

  When the scanning signal of the scanning line 105 is applied by sequential scanning, the pixel 103 connected to the applied scanning line 105 emits light according to the image data signal. In the passive matrix method, there is no active element in the pixel 103, and the manufacturing cost can be reduced.

[Lighting device]
The organic EL material according to the present invention can also be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescence or phosphorescence, and the light emission. Any combination of a dye material that emits light from the material as excitation light may be used, but in the white organic EL device according to the present invention, a method of combining a plurality of light-emitting dopants is preferable.

  As a layer structure of the organic EL element for obtaining a plurality of emission colors, a method of having a plurality of emission dopants in one emission layer, a plurality of emission layers, and an emission wavelength of each emission layer. Examples thereof include a method in which different dopants are present, and a method in which minute pixels that emit light at different wavelengths are formed in a matrix.

  In the white organic EL element concerning this invention, you may pattern by a metal mask, the inkjet printing method, etc. as needed at the time of film-forming. When patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.

  The light emitting material used for the light emitting layer is not particularly limited. For example, in the case of a backlight in a liquid crystal display element, the platinum complex according to the present invention is known so as to be suitable for the wavelength range corresponding to the CF (color filter) characteristics. Any one of the light emitting materials may be selected and combined to be whitened.

  Thus, in addition to the display device and the display, the white light-emitting organic EL element is used as a liquid crystal display as a kind of lamp such as various light-emitting light sources and lighting devices, home lighting, interior lighting, and exposure light source. It is also useful for display devices such as device backlights.

  In addition, light sources such as billboard advertisements, traffic lights, optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc., and general household appliances that require display devices A range of uses is mentioned.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Examples 1-4, Comparative Examples 1-3
The following coating solution was prepared.
(1) Coating liquid tetraethoxysilane hydrolyzate * 27 g
γ-methacryloxypropyltrimethoxysilane 0.8 g
Aluminum trisethyl acetoacetate 0.8g
50 ml of cyclohexanone
Fluorosurfactant 0.1g
(Megafuck F-172, manufactured by Dainippon Ink and Company)
* Preparation method of tetraethoxysilane hydrolyzate 380 ml of ethanol was added to 250 g of tetraethoxysilane, and an aqueous hydrochloric acid solution prepared by dissolving 3 g of hydrochloric acid (12 mol / liter) in 235 g of water was slowly added dropwise to this solution at room temperature. After dropping, the mixture was stirred for 3 hours at room temperature.
(2) Coating film forming method As a resin film base material, the coating liquid is applied with a bar coater on a PEN film (thickness 150 μm) with an acrylic clear hard coat layer (5 μm) and dried at 80 ° C. for 5 minutes. It was. Next, after irradiating with a high pressure mercury lamp (80 W) with ultraviolet rays at an irradiation dose of 0.5 W / cm ² for different irradiation times, corona discharge generated by a high frequency power source of 40 kHz was further applied at an irradiation dose of 0.3 W / cm ^2. Irradiation was performed after changing the irradiation time. A silicon oxide film having a thickness of 500 nm was formed on the resin film substrate. (Examples 1-4 and Comparative Examples 1-3)
As a result of measuring the water vapor transmission rate and the oxygen transmission rate of the obtained gas barrier film with an oxygen transmission rate measuring device OX-TRAN2 / 21 · L type and a water vapor transmission rate measuring device PERMATRAN-W3 / 33G type manufactured by Mocon Co., Ltd. Is shown in Table 1.

  The oxygen permeability and water vapor permeability were greatly improved in the case where the energy treatment was performed, compared to the case where the energy treatment was not performed. Further, it can be seen that the oxygen permeability and water vapor permeability are clearly improved in the case of using both in combination as compared with the comparative example in which only the ultraviolet treatment or the corona discharge treatment was performed as the energy treatment.

Example 5
Using the gas barrier film sample produced in Example 4, an organic EL device was produced by the following method.
A transparent conductive film was produced on the ceramic film by the following method.

<Formation of transparent conductive film>
First, a transparent conductive thin film was formed on the gas barrier film (silicon oxide film) of the gas barrier film produced in Example 4 by an atmospheric pressure plasma method.

  The plasma discharge apparatus used for forming the transparent conductive thin film was a parallel plate type electrode, the transparent film was placed between the electrodes, and a mixed gas was introduced to form a thin film.

  In addition, as a ground (ground) electrode, a 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried. The electrode was cured by ultraviolet irradiation and sealed, and the dielectric surface thus coated was polished, smoothed, and processed to have an Rmax of 5 μm. Further, as the application electrode, an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used. A plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space.

Moreover, as a power source used for plasma generation, a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and 5 W / cm ² of power was supplied at a frequency of 13.56 MHz.

A mixed gas having the following composition is caused to flow between the electrodes to form a plasma state, and the above gas barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film having a thickness of 100 nm is formed on the gas barrier layer (ceramic film). The film was formed.
Discharge gas: Argon 98.5% by volume
Reactive gas 1: Hydrogen 0.25 volume%
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
(Production of organic EL element)
The gas barrier film 100 mm × 100 mm on which the ITO film is formed is used as a substrate. After patterning, the gas barrier film substrate provided with the ITO transparent electrode is ultrasonically cleaned with isopropyl alcohol and dried with dry nitrogen gas. did. This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD is put in a molybdenum resistance heating boat, and 200 mg of CBP as a host compound is put in another resistance heating boat made of molybdenum. 200 mg of bathocuproin (BCP) was put in a molybdenum resistance heating boat, 100 mg of Ir-1 was put in another resistance heating boat made of molybdenum, and 200 mg of Alq ₃ was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus. .

Next, the pressure in the vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, and the heating boat containing α-NPD is energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. Was provided. Further, the heating boat containing CBP and Ir-1 was energized and heated, and co-evaporated on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively, to provide a light emitting layer. . In addition, the substrate temperature at the time of vapor deposition was room temperature. Furthermore, the heating boat containing BCP was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer. Further, the heating boat containing Alq ₃ is further energized and heated, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second, and an electron transport layer having a thickness of 40 nm is further provided. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element was produced.

(Preparation of sealing film)
Polypropylene is laminated with a film thickness of 30 μm on one side of an aluminum foil with a film thickness of 30 μm, and a gas barrier film made of silicon oxide is formed on the opposite surface by a sol-gel method in the same manner as in Example 4. (50 nm) to produce a sealing film.

  In an environment purged with nitrogen gas (inert gas), an epoxy adhesive is used, and the surface of the sealing film provided with the silicon oxide film and the cathode surface of the organic EL element are used as a substrate. The organic EL device 1 was fabricated by sealing the gas barrier film around the area where the organic EL element was not formed, thereby sealing the element (FIG. 8).

(Evaluation of organic EL elements)
The produced organic EL element was energized at a high temperature and high humidity of 60 ° C. and 95% RH, and the occurrence of dark spots was observed.

  It turned out that the organic EL device produced by the sealing method of the present invention is excellent in sealing performance and hardly generates dark spots.

It is a figure which shows an example of a microwave irradiation apparatus. It is a figure which shows an example of a flame plasma processing apparatus. It is a schematic diagram which shows the structure of the transparent gas barrier film of this invention. It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the jet system useful for this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the system which processes a base material between counter electrodes useful for this invention. It is a perspective view which shows an example of the structure of the electroconductive metal base material of the roll rotating electrode shown in FIG. 3, and the dielectric material coat | covered on it. It is a perspective view which shows an example of the structure of the electroconductive metal preform | base_material of a rectangular tube type electrode, and the dielectric material coat | covered on it. It is a section schematic diagram of an organic EL device sealed using a gas barrier film of the present invention. It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. 4 is a schematic diagram of a display unit A. FIG. It is a schematic diagram of a pixel. It is a schematic diagram of the display apparatus by a passive matrix system.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 Gas barrier film 3 Ceramic film Y Resin film base material 10, 30 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 14 Processing position 21, 41 1st power supply 22, 42 2nd power supply 32 Discharge space (counter electrode) while)
35 Roll rotating electrode (first electrode)
35a Roll electrode 35A Metal base material 35B, 36B Dielectric 36 Square tube type fixed electrode group (second electrode)
36a Rectangular tube electrode 36A Metal base material 40 Electric field applying means 50 Gas supply means 52 Air supply port 53 Air exhaust port F Base material G Gas G ° Gas in plasma state

Claims (5)

A gas barrier film having a gas barrier layer having a film density of 2 g / cm ³ or more on a resin film, wherein the gas barrier layer is formed by applying a coating liquid and then drying and densifying by energy treatment. A gas barrier film characterized by that. The gas barrier film according to claim 1, wherein the gas barrier layer is formed by applying and drying a coating liquid containing a metal alkoxide hydrolysis and polycondensation liquid. 3. The energy treatment according to claim 1, wherein any one of a corona discharge treatment, a plasma discharge treatment, and a flame plasma treatment is combined in addition to any of ultraviolet treatment, electron beam treatment, and microwave treatment. Gas barrier film. A resin substrate for organic electroluminescence, wherein a transparent conductive thin film is formed on the gas barrier film according to claim 1. A phosphorescent light emitting organic electroluminescent material film and a metal film serving as a cathode are coated on the organic electroluminescent resin substrate according to claim 7, and a resin-laminated metal foil is further adhered and sealed with an adhesive. An organic electroluminescence element.

Images