JP4835031B2 - Method for producing gas barrier film, method for producing organic electroluminescence resin substrate, and method for producing organic electroluminescence element - Google Patents

Description

  The present invention relates to a method for producing a gas barrier film having a novel laminated structure, a method for producing a resin substrate for organic electroluminescence using the same, and a method for producing an organic electroluminescent element.

  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 resin film made of polyvinylidene chloride resin, 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 resin films, which have been applied to liquid crystal display elements, organic electroluminescence (hereinafter abbreviated as organic EL) elements, etc., have recently been required to be lighter and larger, and have long-term reliability and shape. In addition to the high demands such as high degree of freedom and the ability to display curved surfaces, film base materials such as transparent plastics have begun to be used in place 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. As a gas barrier film used for a packaging material or a liquid crystal display element, a film obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) or a film obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). These are currently known to have water vapor barrier properties of about ² g / m ² / day or 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.
Japanese Patent Publication No.53-12953 JP 58-217344 A US Pat. No. 6,268,695

  The present invention has been made in view of the above-mentioned problems, and its purpose is that there is no mixing of impurity particles, enables very stable production, and has excellent adhesion even when stored in a harsh environment. Another object of the present invention is to provide a method for producing a gas barrier film having excellent transparency and gas barrier resistance, a method for producing a resin substrate for organic electroluminescence using the same, and a method for producing an organic electroluminescence element.

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

(Claim 1)
In the method for producing a gas barrier film in which an adhesive film, a ceramic film, and a protective film are sequentially formed on the resin film from the resin film side, the adhesive film, the ceramic film, and the protective film are silicon oxide films, and the same composition All layers of the adhesion film, the ceramic film, and the protective film are supplied to the discharge space with a gas containing a thin film forming gas and a discharge gas under atmospheric pressure or a pressure in the vicinity thereof, and the discharge space is supplied to the discharge space. Exciting the gas by applying a high-frequency electric field, forming the thin film on the substrate by exposing the substrate to the excited gas, and forming the thin film on the substrate, the discharge gas is nitrogen gas, The high frequency electric field applied to the discharge space is a superposition of the first high frequency electric field and the second high frequency electric field, and the density of the adhesion film is 1.85 to 2.00. There is from 2.05 to 2.20, the production method of the gas barrier film density of the protective film is characterized in 1.85 to 2.00 der Rukoto.

(Claim 2 )
Before SL first high-frequency electric field higher frequency ω2 of the second high-frequency electric field than the frequency ω1 of the first high frequency electric field intensity V1, the strength of the strength V2 and discharge start electric field of the second high-frequency electric field is the relationship between the IV, according to claim 1, wherein satisfying the relation V1 ≧ IV> V2 or V1> IV ≧ V2, that the output density of the second high frequency electric field is 1W / cm ² or more Of producing a gas barrier film.

(Claim 3 )
A film having a claim 1 or 2, the gas-barrier unevenness on the protective film of the gas barrier film produced by the method of producing a film according to provided further refractive index film formation with sol-gel reaction thereon 1.9 As mentioned above, the manufacturing method of the resin base material for organic electroluminescence characterized by providing a high-refractive-index film of 2.1 or less by the wet coating method, and also forming a transparent conductive film on it.

(Claim 4 )
On the resin substrate for organic electroluminescence manufactured by the method for manufacturing a resin substrate for organic electroluminescence according to claim 3 , a phosphorescent organic electroluminescence material and a metal film serving as a cathode are provided and sealed. A method for producing an organic electroluminescence device characterized in that:

  According to the present invention, a gas barrier film that does not contain impurity particles, enables extremely stable production, has excellent adhesion even when stored in a harsh environment, and has good transparency and gas barrier resistance. The manufacturing method of this, the manufacturing method of the resin base material for organic electroluminescence using the same, and the manufacturing method of an organic electroluminescent element can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the inventor of the present invention, in the gas barrier film manufacturing method for sequentially forming an adhesive film, a ceramic film and a protective film on the resin film from the resin film side, The ceramic film and the protective film are silicon oxide films and are formed using the same composition, and all of the adhesion film, the ceramic film and the protective film are formed into a thin film in the discharge space under atmospheric pressure or in the vicinity thereof. A gas containing a gas and a discharge gas is supplied, a high frequency electric field is applied to the discharge space to excite the gas, and the substrate is exposed to the excited gas to form a thin film on the substrate. The discharge gas is nitrogen gas, the high frequency electric field applied to the discharge space is formed by superimposing the first high frequency electric field and the second high frequency electric field, and the adhesion film is densely formed. There is from 1.85 to 2.00, the density of the ceramic film is from 2.05 to 2.20, the gas barrier properties of the density of the protective film is characterized in 1.85 to 2.00 der Rukoto Gas barrier film with excellent transparency and gas barrier resistance, which can be manufactured in a stable manner without contamination by impurity particles, and has excellent adhesion even when stored in harsh environments, depending on the film manufacturing method. As a result, the present invention has been found.

  Details of the present invention will be described below.

In the method for producing a gas barrier film of the present invention, in the method for producing a gas barrier film in which an adhesion film, a ceramic film, and a protective film are sequentially formed on the resin film from the resin film side, the adhesion film, the ceramic film, and The protective film is a silicon oxide film formed using the same composition, and all of the adhesion film, the ceramic film, and the protective film are formed into a thin film forming gas in the discharge space under atmospheric pressure or in the vicinity thereof. And a gas containing a discharge gas, a high frequency electric field is applied to the discharge space to excite the gas, and the substrate is exposed to the excited gas to form a thin film on the substrate The high-frequency electric field formed by the forming method, wherein the discharge gas is nitrogen gas, and applied to the discharge space is an atmospheric pressure plasma in which the first high-frequency electric field and the second high-frequency electric field are superimposed. Characterized in that it is formed by using the VD device.

In general wet methods such as spraying and spin coating methods, it is difficult to obtain smoothness at the molecular level (nm level), and since a solvent is used, in the resin film applied in the present invention, usable groups are used. There is a disadvantage that the material or solvent is limited. Therefore, in the present invention, by using the atmospheric pressure plasma CVD method, a vacuum chamber or the like is unnecessary, a high deposition method productivity can high-speed film is obtained. This is because by forming the adhesion film, the ceramic film, and the protective film by the atmospheric pressure plasma CVD method, it is possible to relatively easily form a film having a uniform and smooth surface. Details of the conditions for forming each thin film by the plasma CVD method will be described later.

In the thin film formation by the atmospheric pressure plasma CVD method as described above, the thin film forming gas mainly includes a raw material gas for forming a thin film, a decomposition gas for decomposing the raw material gas to obtain a thin film forming compound, and It is comprised from the discharge gas for setting it into a plasma state. In the conventional method, when forming a plurality of thin layers while laminating, when forming each thin layer, the thin film forming gas is sequentially used by using each thin film forming gas containing a raw material gas having a different composition. While the laminated body was formed using the same plasma discharge generator while exchanging, in this method, when a desired thin film was formed, it was caused by the residual of the source gas etc. on which the thin film was formed before that. Contamination or mixing of different kinds of composition particles such as impurity particles adhering to the wall of the apparatus has been a major obstacle in forming a highly homogeneous thin film.

In the present invention, in order to solve the above-mentioned problems, when the adhesion film, the ceramic film and the protective film are sequentially formed on the resin film, the adhesion film, the ceramic film and the protective film are formed by forming a silicon oxide having the same composition. It is characterized by using forming gas, and as a result, there is no mixing of impurity particles, it enables very stable production, and it has excellent adhesion even when stored in harsh environments, and good transparency A gas barrier film having gas barrier resistance can be produced.

  In the method for producing a gas barrier film of the present invention, there is no particular limitation on a method for forming an adhesion film, a ceramic film and a protective film having a desired structure using a thin film forming gas composed of the same composition. However, it is possible to select the optimal raw materials and appropriately select the composition ratio of the source gas, decomposition gas and discharge gas, the supply rate of the thin film forming gas to the plasma discharge generator, or the output conditions during the plasma discharge treatment, etc. preferable.

  In the adhesion film, ceramic film and protective film according to the present invention composed of the same composition, separation between thin films, or as a confirmation method, for example, density difference between each thin layer, content difference of raw material compounds, The adhesion film, the ceramic film, and the protective film can be separated by measuring the hardness difference of each thin film or the carbon content difference related to the density.

In the method for producing a gas barrier film of the present invention, the density of the ceramic layer, be set higher than the respective density of the adhesion film and the protective film located above and below, specifically, the density of the adhesive film 1 One of the characteristics is that the density of the ceramic film is 2.05 to 2.20, and the density of the protective film is 1.85 to 2.00 .

  The density of each constituent layer defined in the present invention can be determined using a known analysis means. In the present invention, the value determined by the X-ray reflectivity method is used.

  The outline of the X-ray reflectivity method is described in page 151 of the X-ray diffraction handbook (Science Electric Co., Ltd., 2000, International Literature Printing Co., Ltd.) 22 can be performed.

  Specific examples of measurement methods useful in the present invention are shown below.

  The measurement is performed using MXP21 manufactured by Mac Science. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting is performed using 1 and each parameter is obtained so that the residual sum of squares of the actually measured value and the footing curve is minimized. The thickness and density of each laminated film can be obtained from each parameter. The film thickness evaluation of each laminated film in the present invention can also be obtained from the above X-ray reflectivity measurement.

  Further, in the gas barrier film according to the present invention, the low density film has a correlation with the high carbon-containing film, and the high density film has a correlation with the low carbon-containing film. The boundary part of each layer can be confirmed by the content difference.

  In the present invention, the carbon content of each thin film can be determined using known analysis means.

  In the present invention, the atomic number concentration indicating the carbon content is calculated by the following XPS method and is defined below.

Atomic concentration% = number of carbon atoms / number of all atoms × 100
In the present invention, the XPS surface analyzer used ESCALAB-200R manufactured by VG Scientific. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement, first, the range of the binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

  Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) so as not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as the atomic concentration (at%).

  Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

  Next, components of the gas barrier film according to the present invention will be described.

<< Adhesion film, ceramic film and protective film >>
First, an adhesion film, a ceramic film, and a protective film (hereinafter collectively referred to as a gas barrier layer) according to the present invention will be described.

The gas barrier layer according to the present invention, the layer der each of the thin film blocking transmission of oxygen and water vapor is, as the material constituting the gas gas barrier layer, characterized in that it is a silicon oxide. Further, the thickness of the gas barrier layer 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 1 to 1000 nm. This is because if the thickness of the gas barrier layer is thinner 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 layer is larger than the above range, it is difficult to maintain the flexibility of the gas barrier film, and the gas barrier film cracks due to external factors such as bending and pulling after film formation. This is because there is a risk of occurrence.

The gas barrier layer obtained by the plasma CVD method under atmospheric pressure or near atmospheric pressure is made by selecting conditions such as organometallic compound, decomposition gas, decomposition temperature, and input power as raw materials (also referred to as raw materials). Carbides, metal nitrides, metal oxides, metal sulfides, metal halides, and mixtures thereof (such as metal oxynitrides, metal oxyhalides, and metal nitride carbides) can be formed separately, which is preferable.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such an inorganic material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

As such an organometallic compound,
As silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, Diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethyl Amino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylaminoto Methylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris ( Dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3 -Disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltri Tylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane , Hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

In the gas barrier layer according to the present invention, inorganic compounds containing the gas barrier layer, characterized in that an oxidation silicofluoride-containing, in particular, moisture permeability, light transmittance and viewpoint et effective atmospheric pressure plasma CVD suitability to be described later It is .

  The inorganic compound according to the present invention can obtain, for example, a film containing at least one of O atoms and N atoms and Si atoms by further combining oxygen gas and nitrogen gas at a predetermined ratio with the organic silicon compound. .

  Therefore, the gas barrier layer according to the present invention is preferably transparent. This is because when the gas barrier layer is transparent, the gas barrier film can be made transparent, and can be used for applications such as a transparent substrate of an organic EL element.

<Resin film>
The base material used in the gas barrier film according to the present invention is not particularly limited as long as it is a resin film capable of holding the above-described gas barrier layer having the 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.

  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 Limited), Konicatac of cellulose triacetate film Commercially available products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  The resin film is preferably transparent. Since the resin film is transparent and the gas barrier layer formed on the resin film is also transparent, a transparent gas barrier film can be obtained, and thus a transparent substrate such as an organic EL element can be obtained. Because.

  The resin film listed above may be an unstretched film or a stretched film.

  The resin film according to 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.

  In addition, the resin film according to the present invention may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, and chemical treatment before forming the vapor deposition film.

Further, an anchor coating agent layer may be formed on the surface of the resin film 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 the resin film 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).

  As the resin film, a long product wound up in a roll shape is convenient. The thickness of the resin film varies depending on the use of the resulting gas barrier film, so it cannot be specified unconditionally. However, when the gas barrier film is used as a packaging application, there is no particular limitation, and it is suitable for packaging materials. 3 to 400 [mu] m, preferably 6 to 30 [mu] m.

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

As the water vapor permeability of the gas barrier film of the present invention, the water vapor permeability measured according to the JIS K7129 B method when used for an application requiring high water vapor barrier properties such as an organic EL display and a high-definition color liquid crystal display, It is preferably 1 × 10 ⁻³ g / m ² / day or less, and in the case of an organic EL display application, a dark spot that grows even if it is extremely small, and the display life of the display becomes extremely short. In some cases, the water vapor permeability is preferably less than 1 × 10 ⁻⁵ g / m ² / day.

<Plasma CVD method>
Next, as a method for producing a transparent gas barrier film of the present invention, a plasma CVD method and an atmospheric pressure plasma CVD method that can be suitably used for forming a low density layer, a medium density layer and a high density layer according to the present invention, Further details will be described.

  The plasma CVD method according to the present invention will be described.

  The plasma CVD method is also called a plasma-assisted chemical vapor deposition method or PECVD method, and various inorganic materials can be applied in a three-dimensional form with good coverage and adhesion, and without excessively increasing the resin film temperature. This is a technique capable of forming a film.

  In the usual CVD method (chemical vapor deposition method), the volatile and sublimated organometallic compound adheres to the surface of the high-temperature resin film, and a thermal decomposition reaction occurs, producing a thermally stable inorganic thin film. That's it. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and cannot be used for forming a film on a plastic substrate.

  On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the resin film to generate a space (plasma space) where a gas in a plasma state exists, and the volatile / sublimated organometallic compound is introduced into the plasma space. Then, after the decomposition reaction has occurred, it is sprayed onto the resin film to form an inorganic thin film. 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, the resin film for forming the inorganic substance can also be lowered in temperature, and is a film forming method capable of sufficiently forming a film on a plastic substrate.

  However, in the plasma CVD method, it is necessary to ionize the gas by applying an electric field to the gas, and since the film is usually formed in a reduced pressure space of about 0.101 kPa to 10.1 kPa, a large area is required. When forming the film, the equipment is large and the operation is complicated, and this method has a problem of productivity.

On the other hand, in the plasma CVD method near atmospheric pressure according to the present invention, it is not necessary to reduce the pressure and the productivity is high as compared with the plasma CVD method under vacuum, and the plasma density is high. The film forming speed is high, and furthermore, under the high pressure condition under atmospheric pressure compared with the normal conditions of the CVD method, the mean free path of gas is very short, so that an extremely flat film is obtained. A flat film has good optical properties and gas barrier properties. From the above, the present invention is characterized by applying the atmospheric pressure plasma CVD method.

In the method for producing a gas barrier film of the present invention, a gas containing a thin film forming gas and a discharge gas is supplied to a discharge space under atmospheric pressure or a pressure near the atmospheric pressure, and a high frequency electric field is applied to the discharge space. by exciting the gas, exposed to the gas to excite the substrate in how to form a thin film on the substrate, a discharge gas is nitrogen gas, a high frequency electric field applied to the discharge space, the the thin film forming method obtained by superimposing the first high frequency electric field and the second high frequency electric field, on a resin film, adhesive film, and forming all the layers of the ceramic film and the protective film.

Further, the first high-frequency electric field higher frequency ω2 of the second high-frequency electric field than the frequency ω1 of the intensity V1 of the first high frequency electric field, the second high frequency electric field strength V2 and discharge starting electric field The object of the present invention is that the relationship with the strength IV satisfies the relationship of V1 ≧ IV> V2 or V1> IV ≧ V2 and the output density of the second high-frequency electric field is 1 W / cm ² or more. It is preferable from the viewpoint of performance.

  Hereinafter, an apparatus for forming a gas barrier layer using a plasma CVD method at or near atmospheric pressure will be described in detail.

  In the method for producing a transparent gas barrier film of the present invention, an example of a plasma film forming apparatus used for forming an adhesion film, a ceramic film and a protective film will be described with reference to FIGS. In the figure, symbol F is a long film as an example of a resin film.

  FIG. 1 is a schematic view showing an example of a jet type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

  In addition to the plasma discharge processing apparatus and the electric field applying means having two power sources, the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. And an electrode temperature adjusting 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 supply 21 is output from the first electrode 11 between the counter electrodes. A first high frequency electric field having electric field strength V ₁ and current I ₁ is applied, and a second high frequency electric field having frequency ω ₂ , electric field strength V ₂ and current I ₂ from second power source 22 is applied from 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.

  Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge processing apparatus of the present invention has a capability of applying a higher frequency voltage than the second power source.

  As a discharge condition in the present invention, a high frequency voltage is applied between the opposed first electrode 11 and second electrode 22, and the high frequency voltage superimposes the first high frequency voltage V1 and the second high frequency voltage V2. When the discharge start voltage is IV, V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied. More preferably, V1> IV> V2 is satisfied.

  Here, the high frequency voltage (applied voltage) and the discharge start voltage in the present invention are those measured by the following method.

Measuring method of high-frequency voltages V1 and V2 (unit: kV / mm):
A high-frequency probe (P6015A) for each electrode part is installed, and the high-frequency probe is connected to an oscilloscope (Tektronix, TDS3012B) to measure the voltage.

Measuring method of discharge start voltage IV (unit: kV / mm):
A voltage at which discharge gas is supplied between the electrodes and discharge starts is defined as a discharge start voltage IV. The measuring instrument is the same as the above high-frequency voltage measurement.

  The positional relationship between the high-frequency probes 25 and 26 and the oscilloscopes 27 and 28 used for the measurement is shown in FIG.

  By taking such a discharge condition, for example, even a discharge gas having a high discharge start voltage such as nitrogen gas can start discharge and maintain a high density and stable plasma state. A high-performance transparent conductive film can be formed.

  When the discharge gas is nitrogen gas according to the above measurement, the discharge start voltage IV is about 3.7 kV / mm. Therefore, in the above relationship, the first high-frequency voltage is set as V1 ≧ 3.7 kV / mm. By applying this, nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a sine wave or a pulse. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and good-quality transparent conductive film can be obtained. The upper limit is preferably about 200 MHz.

  Application of a high-frequency voltage from such two power sources is necessary to start discharge of a discharge gas having a high discharge start voltage on the first frequency ω1 side, and the second frequency ω2 side is plasma. It is an important point of the present invention that it is necessary to increase the density and form a dense and good quality gas barrier layer.

  A gas G is introduced into a gap (discharge space) 13 between the first electrode 11 and the second electrode 12 from a gas supply means as shown in FIG. 2 to be described later, and the first electrode 11 and the second electrode A processing space created by the lower surface of the counter electrode and the resin film 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 an unwinded resin film (unwinder) and conveyed, or processed on the resin film F conveyed 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 resin film 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 resin film 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, they 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. 2 is a schematic configuration diagram showing another example of a plate electrode type atmospheric pressure plasma processing apparatus preferably used in the present invention. A counter electrode (discharge space) is formed by the movable gantry electrode (first electrode) 8 and the square electrodes (second electrodes) 11 and 12, a high frequency electric field is applied between the electrodes, and the discharge gas and the thin film forming gas are contained. A gas G is supplied through a gas supply pipe, passes through a slit 13 formed between the rectangular electrodes 11 and 12, flows out into the discharge space, excites the gas G by discharge plasma, and is placed on the movable gantry electrode 8. By exposing the surface of F to the excited gas G ′, a thin film is formed on the substrate surface.

  FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus that treats a resin film between counter electrodes useful in 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. 3 shows a thin film formed by plasma discharge treatment of the resin film F in the counter electrode (discharge space) 32 between the roll rotating electrode (first electrode) 35 and the rectangular tube type fixed electrode group (second electrode) 36. To do. In FIG. 4, one electric field is formed by a pair of rectangular tube type fixed electrode group (second electrode) 36 and roll rotating electrode (first electrode) 35, and this one unit, for example, a low density layer The formation of. FIG. 4 shows a configuration example including a total of five units having such a configuration, and by arbitrarily independently controlling the type of raw material to be supplied, the output voltage, etc. in each unit, A laminated transparent gas barrier layer having a configuration defined in the present invention can be continuously formed.

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. 41 to the first high-frequency electric field of frequency ω ₁ , electric field strength V ₁ , and current I ₁ , and the rectangular cylindrical fixed electrode group (second electrode) 36 has a frequency ω ₂ A second high frequency electric field of electric field strength V ₂ and 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. In addition, 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 to the second electrode from the second power source 42. 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 while controlling the flow rate.

  The resin film F is unwound from the original winding (not shown), or is transported from the previous process, or transported from the previous process, and the air entrained by the resin film is blocked by the nip roll 65 via the guide roll 64 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 resin film 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 resin film 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. 4 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 3 and the dielectric material coated thereon.

  In FIG. 4, 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. 5 is a perspective view showing an example of the structure of a conductive metallic base material of a rectangular tube electrode and a dielectric material coated thereon.

  In FIG. 5, a rectangular tube type electrode 36a has a coating of a dielectric 36B similar to FIG. 4 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. 5 may be a cylindrical electrode, but the rectangular tube electrode has an effect of widening the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .

  4 and 5, 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 0.5 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 of the parallel electrodes (up to the vicinity of the resin film surface) with an object made of the material as described above.

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
Can be mentioned, 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. be able to. Thereby, the further uniform high-density plasma can be produced | generated and the improvement of the film forming speed and the improvement of film quality can be made compatible. 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.

  In addition, when the film quality is controlled in the present invention, it can also be achieved by controlling the power on the second power source side.

  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 long-term use 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.

  Subsequently, the manufacturing method of the organic electroluminescent resin base material of this invention is demonstrated.

  In the method for producing a resin substrate for organic electroluminescence according to the present invention, a film having an uneven shape is provided on the protective film of the gas barrier film produced according to the above-described method, and a film is formed thereon by a sol-gel reaction. A high refractive index film having a refractive index of 1.9 to 2.1 is provided by a wet coating method, and a transparent conductive film is further formed thereon.

  The light extraction efficiency is improved by the film having an uneven shape according to the present invention and the smooth high refractive index film having a refractive index of 1.9 or more and 2.1 or less.

  Since the refractive index n of the film having an uneven shape according to the present invention is generally about 1.45 to 1.60, the refractive index of the gas barrier film having an adhesion film, a ceramic film and a protective film on the resin film. It is preferable that it is equivalent.

  On the other hand, the thickness of the film having a concavo-convex shape is preferably equal to or greater than the wavelength of light emitted from the organic EL light emitting layer, from the effect of diffraction. This is because when the thickness of the film having a concavo-convex shape is about the wavelength of the light to be emitted, the concavo-convex shape due to diffraction is equal to or less than the thickness at which light as an electromagnetic wave exuded by evanescent enters the gas barrier film. This is because the effect of the film having the thickness is reduced.

  Therefore, in order to sufficiently exhibit the diffraction effect in the film having the uneven shape, it is preferable to set it to 3 times or longer, which is sufficiently longer than the center wavelength. The upper limit of the thickness is not particularly limited from the viewpoint of effect, but is preferably about 20 μm from the viewpoint of manufacturing.

  Next, the uneven shape will be described. As a method for generating the scattering effect, for example, there is a method of randomly arranging irregularities with a random period. Light incident on the random irregularities on the surface of the film is divided into transmitted light and reflected light. The transmitted light is taken into the film having an uneven shape as described above, and the reflected light is incident on the random unevenness again by reflection by the cathode, and finally is taken out to the film having the uneven shape.

  In this case, changing the traveling direction of light to a direction that does not follow the law of diffraction is the same as that of the diffraction grating described above, but the change in the traveling direction of light by the relief type diffraction grating has regularity. In the case of this random unevenness, there is no regularity in the change of the traveling direction of light. Therefore, the observer feels that the viewing angle of the light emitting surface of the organic EL element is relatively wide.

  The random irregularities described above have a sufficient scattering effect when the diameter of a circle circumscribing a shape formed by projecting a concave or convex portion on the film surface is 0.2 μm or more. This is because of the relationship between the distance between the shortest centers of the circles and the wavelength of light in the medium in a state where circles having a diameter of 0.2 μm are spread. In addition, although the diameter of the circumscribed circle of the projected shape depends on the projected shape, it is expected that the unevenness can be visually confirmed through the transparent substrate 201 when the diameter is close to 100 μm, and it is expected to cause discomfort to the observer. In order to prevent this, the diameter is preferably 50 μm or less. Therefore, the diameter of the circumscribed circle of the projection shape is preferably 0.2 μm or more and 50 μm or less.

  Further, the shape of the projected shape is not particularly limited to a circle or a polygon, and the cross-sectional shape of the unevenness in the depth direction may be a U shape, a V shape, a column shape such as a cylinder, and the like, and is not particularly limited.

  Moreover, when the depth of the random unevenness is 100 nm or more, a sufficient scattering effect can be obtained. Furthermore, the upper limit of the depth is not particularly limited from the viewpoint of the effect, but if it becomes too deep, it becomes difficult to manufacture, and therefore it is preferably not more than twice the diameter of the circumscribed circle of the projected shape. Therefore, the depth range is preferably 100 nm or more and not more than twice this diameter.

  In addition, the ratio of the area of the entire surface on which the unevenness is provided to the projected area of the concave portion or convex portion is preferably about 10% to 90%.

  As a material for forming a film having a concavo-convex shape according to the present invention, in consideration of facilitating the formation of the concavo-convex shape, for example, a fluorine resin, an acrylic resin, an epoxy resin, an airgel, porous silica Etc.

  As a method for forming the unevenness, for example, there is a method of forming in the course of a general resin molding method or a sol-gel method.

  For example, a photoresist is applied to a glass substrate using a spin coat method or the like, and patterning is performed using general mask exposure, electron beam, interference exposure, or the like. Then, what etched the glass substrate is made into a glass type | mold, By using this glass type | mold, an unevenness | corrugation can be formed with the following methods, for example.

(1) Form a film having a concavo-convex shape with a photocurable resin As a film having a concavo-convex shape on a gas barrier film, for example, after directly applying a UV curable resin, which is one of the photocurable resins, It presses using said glass type | mold, the state is maintained, resin is hardened by UV irradiation, and an unevenness | corrugation is shape | molded.

(2) Form a film having a concavo-convex shape with a thermosetting or thermoplastic resin After directly applying a thermosetting resin as a film on a gas barrier film, press-mold with the above glass mold, and then heat cure. To form irregularities.

  In the case of a thermoplastic resin, the above-described press molding is replaced with hot press molding, and then cooled to form irregularities. This glass mold may be transferred to a mold by a method such as nickel electroforming.

(3) Forming a film having a concavo-convex shape by a sol-gel method A liquid sol is directly applied as a film on a gas barrier film and then press-molded using the glass mold of (2) above. Then, it is dried by heating or the like to form irregularities as a dry gel. This glass mold may be transferred to a mold by a method such as nickel electroforming.

  In the method for producing a gas barrier film of the present invention, a high refractive index film having a refractive index of 1.9 or more formed by a sol-gel reaction is formed on the upper part of the film having the above-described uneven shape by a wet coating method. It is characterized by providing.

  The refractive index of the high refractive index film according to the present invention is 1.90 or more and 2.1 or less, preferably 1.90 to 2.1. The thickness of the high refractive index film is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index film is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index film is preferably H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

  In the high refractive index film according to the present invention, a refractive index formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula (1) The layer is preferably 1.90 or more.

General formula (1)
Ti (OR ₁ ) ₄
In the formula, R ₁ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These can be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  The present invention is characterized in that a high refractive index film is provided by a wet coating method, but the coating liquid for high refractive index film used for the formation is the above in a solution in which water and an organic solvent described later are sequentially added. It is preferable to add an organic titanium compound. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent according to the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably accounts for 50.0 to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50 to 90% by mass, and further preferably 55 to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index film according to the present invention contains metal oxide particles as fine particles, and further contains a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index film preferably have a refractive index of 1.90 to 2.80, and more preferably 1.90 to 2.70. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index film in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The high refractive index film according to the present invention preferably uses a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable. (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  Next, the transparent conductive film according to the present invention will be described.

  The method for producing a resin substrate for organic electroluminescence according to the present invention is characterized in that a transparent conductive film serving as an anode of an organic electroluminescence element is further formed on a high refractive index film provided by a wet coating method.

  The transparent conductive film according to the present invention can be obtained by a vapor deposition method, a plasma CVD method, a plasma CVD method under the above-described atmospheric pressure or a pressure near atmospheric pressure, or the like. It can also be obtained by a sol-gel method (coating method) or the like.

However, it is preferably formed by the above atmospheric pressure plasma discharge treatment apparatus. For example, industrially, a DC magnetron sputtering apparatus is used and the specific resistance value is excellent in the order of 10 ⁻⁴ Ω · cm. Indium tin oxide (ITO) films can be obtained. In these physical fabrication methods (PVD methods), a target substance is deposited on a substrate in a gas phase to grow the film, and a vacuum vessel is used. Therefore, the apparatus is large and expensive, and the use efficiency of raw materials is poor, so that productivity is low. Moreover, it was difficult to form a film with a large area. Furthermore, in order to obtain a low resistance product, it is necessary to heat to 200 to 300 ° C. during film formation, and it is difficult to form a low resistance transparent conductive film on a resin film.

  The gas used in the formation of the transparent conductive film varies depending on the type of transparent conductive film desired to be provided on the high refractive index film, but basically, a reaction that becomes a plasma state to form the inert gas and the transparent conductive film. It is a mixed gas of sex gas. 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. More preferably, it is a reaction gas selected from the following compounds, for example, 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-t- Examples thereof include 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 transparent 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 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, In addition to the reactive gas containing the constituent elements of the transparent conductive film, water can be used as the reactive gas, so that the transparent conductive having high conductivity and high etching rate can be mentioned. A membrane can be manufactured. 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%.

  As the reactive gas in the present invention, an organic metal compound containing an element constituting the transparent conductive film and water, an oxidizing gas such as oxygen, a reducing gas such as hydrogen, and the like, 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 tetrapentaethoxy. Silane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxy Silane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysila , Dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane, and the like to. 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.

  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 according to 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.

  Subsequently, the manufacturing method of the organic electroluminescent element using the resin base material for organic electroluminescent elements of this invention produced by the said method (henceforth the resin substrate for organic EL) is demonstrated.

  In the method for producing an organic electroluminescence element, a phosphorescent organic electroluminescent material and a metal film serving as a cathode are provided on the resin substrate for organic electroluminescence of the present invention prepared according to the above method and sealed. Thus, an organic electroluminescence element is manufactured.

  Hereinafter, the constituent layers of the organic EL device according to the present invention will be described in detail.

  In the present invention, the phosphorescent organic electroluminescent material (hole transport layer, phosphorescent light emitting layer, hole blocking layer, electron transport layer, anode buffer layer, cathode buffer layer) constituting the organic EL device and the cathode layer configuration are preferable. Specific examples are shown below, but the present invention is not limited thereto.

(1) Organic EL resin substrate containing anode / phosphorescent layer / electron transport layer / cathode (2) Organic EL resin substrate containing anode / hole transport layer / phosphorescent layer / electron transport layer / cathode (3) Organic EL resin substrate containing anode / hole transport layer / phosphorescent layer / hole blocking layer / electron transport layer / cathode (4) Organic EL resin substrate containing anode / hole transport layer / phosphorescent layer / positive Hole blocking layer / electron transport layer / cathode buffer layer / cathode (5) Resin substrate for organic EL containing anode / anode buffer layer / hole transport layer / phosphorescent layer / hole blocking layer / electron transport layer / cathode buffer layer / Cathode (Anode)
The transparent conductive film provided on the outermost layer of the organic electroluminescence resin substrate produced by the above-described method acts as an anode.

  As an anode in an organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound and a mixture thereof having a large work function (4 eV or more) is preferably used. The ratio is desirably 60% or more, 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.

  In the present invention, the cathode made of a metal film also functions as a sealing material for the organic EL element.

  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.

  Typical 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 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.

  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.

  When a DC voltage is applied to the multicolor display device using the organic EL element thus obtained, light emission occurs when a voltage of about 2 to 40 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Observable. 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.

  Illumination devices using organic EL elements according to the present invention include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, and optical communication processors. However, the present invention is not limited to these.

  Further, the organic EL element according to the present invention may be used as an organic EL element having a 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.

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

Example 1
<< Production of gas barrier film >>
[Preparation of gas barrier film 1]
As a resin film, an adhesive layer, a ceramic layer, and a protective layer on a polyethylene naphthalate film having a thickness of 100 μm (a film made by Teijin DuPont, hereinafter abbreviated as PEN) under the following atmospheric pressure plasma discharge treatment apparatus and discharge conditions A gas barrier film 1 having laminated layers was produced.

(Atmospheric pressure plasma discharge treatment equipment)
Using the atmospheric pressure plasma discharge treatment apparatus of FIG. 3, a set of a roll electrode covered with a dielectric and a plurality of rectangular tube electrodes was produced as follows.

  The roll electrode serving as the first electrode is coated with a high-density, high-adhesion alumina sprayed film by an atmospheric plasma method on a jacket roll metallic base material made of titanium alloy T64 having cooling means by cooling water, and roll diameter It was set to 1000 mmφ. On the other hand, the square electrode of the second electrode is a hollow rectangular tube-shaped titanium alloy T64 covered with 1 mm of the same dielectric material with the same thickness under the same conditions, and the opposing rectangular tube-shaped fixed electrode group and did.

Ten square tube electrodes were arranged around the roll rotating electrode with a counter electrode gap of 1 mm. The total discharge area of the rectangular tube type fixed electrode group was 150 cm (length in the width direction) × 4 cm (length in the transport direction) × 10 (number of electrodes) = 6000 cm ² . In all cases, an appropriate filter was installed.

  During plasma discharge, the first electrode (roll rotating electrode) is adjusted to 120 ° C., the second electrode (square tube fixed electrode group) is adjusted to 80 ° C., and the roll rotating electrode is rotated by a drive to form a thin film. went. Among the 10 rectangular tube-shaped fixed electrodes, two from the upstream side are used for forming the following first layer (adhesion layer), and the following six are used for forming the following second layer (ceramic layer). The following two were used for film formation of the third layer (protective layer), each condition was set, and three layers were laminated in one pass.

(First layer: adhesion layer)
Plasma discharge was performed under the following conditions to form an adhesion layer having a thickness of about 50 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 94.5% by volume
Thin film forming gas: hexamethyldisiloxane (abbreviated as HMDSO in Table 1)
(Vaporized by mixing with nitrogen gas with a Lintec vaporizer) 0.5% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed first layer (low density layer) was 1.90 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

(Second layer: Ceramic layer)
Plasma discharge was performed under the following conditions to form a ceramic layer having a thickness of about 30 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: hexamethyldisiloxane (abbreviated as HMDSO in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 10W / cm ²
The density of the formed second layer (ceramic layer) was 2.20 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science.

(3rd layer: protective layer)
Plasma discharge was performed under the following conditions to form a protective layer having a thickness of about 200 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 93.0% by volume
Thin film forming gas: hexamethyldisiloxane (abbreviated as HMDSO in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 2.0% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed third layer (protective layer) was 1.95 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

[Production of gas barrier films 2 and 3]
In the production of the gas barrier film 1, the gas composition ratio and the power supply conditions (discharge conditions) at the time of forming the adhesion layer, the ceramic layer, and the protective layer are appropriately adjusted so that the density of each layer becomes the value described in Table 1. Gas barrier films 2 and 3 were produced in the same manner except for changing to.

[Preparation of gas barrier film 4]
A gas barrier film 4 was produced in the same manner as in the production of the gas barrier film 1 except that the thin film forming gas for the adhesion layer and the protective layer was changed to tetraethoxysilane (abbreviated as TEOS in Table 1).

[Preparation of gas barrier film 5]
A gas barrier film 5 was prepared in the same manner as in the preparation of the gas barrier film 4 except that the thin film forming gas for the adhesion layer was changed to aluminum acetylacetonate (abbreviated as AAA in Table 1).

[Preparation of gas barrier film 6]
In the production of the gas barrier film 1, a gas barrier film 6 was produced in the same manner except that the adhesion layer and the protective layer were formed according to the following method.

(First layer: adhesion layer)
Plasma discharge was performed under the following conditions to form an adhesion layer having a thickness of about 50 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 99.5% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas with a Lintec vaporizer) 0.5% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed first layer (low density layer) was 1.85 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

(3rd layer: protective layer)
Plasma discharge was performed under the following conditions to form a protective layer having a thickness of about 200 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 98.0% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 2.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed third layer (protective layer) was 1.85 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

[Preparation of gas barrier film 7]
In the production of the gas barrier film 1, a gas barrier film 7 was produced in the same manner except that the adhesion layer, the ceramic layer, and the protective layer were formed according to the following method.

(First layer: adhesion layer)
Plasma discharge was performed under the following conditions to form an adhesion layer having a thickness of about 50 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 94.5% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas with a Lintec vaporizer) 0.5% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed first layer (low density layer) was 1.90 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

(Second layer: Ceramic layer)
Plasma discharge was performed under the following conditions to form a ceramic layer having a thickness of about 80 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 10W / cm ²
The density of the formed second layer (ceramic layer) was 2.20 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science.

(3rd layer: protective layer)
Plasma discharge was performed under the following conditions to form a protective layer having a thickness of about 200 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 93.0% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 2.0% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed third layer (protective layer) was 1.95 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

[Preparation of gas barrier film 8]
In the production of the gas barrier film 7, the gas composition ratio and the power supply conditions (discharge conditions) at the time of forming the adhesion layer, the ceramic layer, and the protective layer are appropriately adjusted so that the density of each layer becomes the value described in Table 1. A gas barrier film 8 was produced in the same manner except that it was changed to.

[Preparation of gas barrier film 9]
In the production of the gas barrier film 7, a gas barrier film 9 was produced in the same manner except that the thin film forming gas of the ceramic layer was changed to hexamethylcyclotrisilazane (abbreviated as HMCTS in Table 1).

[Production of Gas Barrier Film 10]
In the production of the gas barrier film 1, a gas barrier film 10 was produced in the same manner except that the adhesion layer, the ceramic layer, and the protective layer were formed according to the following method.

(First layer: adhesion layer)
Plasma discharge was performed under the following conditions to form an adhesion layer having a thickness of about 50 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 96.5% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas with a Lintec vaporizer) 0.5% by volume
Additive gas: 3.0% by volume of hydrogen gas
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed first layer (low density layer) was 1.90 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

(Second layer: Ceramic layer)
Plasma discharge was performed under the following conditions to form a ceramic layer having a thickness of about 30 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 96.9% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 0.1% by volume
Additive gas: 3.0% by volume of hydrogen gas
<Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 10W / cm ²
The density of the formed second layer (ceramic layer) was 2.20 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science.

(3rd layer: protective layer)
Plasma discharge was performed under the following conditions to form a protective layer having a thickness of about 200 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 95.0% by volume
Thin film forming gas: tetramethyldisilazane (abbreviated as TMDS in Table 1)
(Vaporized by mixing with nitrogen gas in a Lintec vaporizer) 2.0% by volume
Additive gas: 3.0% by volume of hydrogen gas
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed third layer (protective layer) was 1.95 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

[Preparation of gas barrier film 11]
In the production of the gas barrier film 10, the gas composition ratio and the power supply conditions (discharge conditions) at the time of forming the adhesion layer, the ceramic layer, and the protective layer are appropriately adjusted so that the density of each layer becomes the value shown in Table 1. A gas barrier film 11 was produced in the same manner except that the gas barrier film 11 was changed to.

[Preparation of gas barrier film 12]
A gas barrier film 12 was produced in the same manner as in the production of the gas barrier film 10 except that the thin film forming gas of the ceramic layer was changed to hexamethylcyclotrisilazane (abbreviated as HMCTS in Table 1).

[Production of gas barrier films 13 and 14]
In the production of the gas barrier films 1 and 3, gas barrier films 13 and 14 were produced in the same manner except that aluminum acetylacetonate was used instead of hexamethyldisiloxane (HMDS) as a thin film forming gas. .

[Preparation of gas barrier film 15]
In the production of the gas barrier film 13, a gas barrier film 15 was produced in the same manner except that the thin film forming gas of the ceramic layer was changed to aluminum isopropoxide (abbreviated as AIP in Table 1).

<< Evaluation of gas barrier film >>
〔quality evaluation〕
(Evaluation of film uniformity)
Elemental analysis by atomic absorption method was performed on 100 points of each of the produced gas barrier film surfaces, composition change due to mixing of different kinds of particles was measured, and film uniformity was evaluated according to the following criteria.

◎: No composition change was observed between 100 points measured ○: Composition change was observed at 1 or 2 points out of 100 measured points, but the quality is acceptable in practice △: Measurement Among the 100 points, the composition change was observed at 3 to 5 points, but the quality was acceptable for practical use. X: Among the 100 points measured, when a clear composition change was observed at 6 points or more, it was practical. The quality in question (assessment of adhesion)
Each gas barrier film produced as described above was evaluated for adhesion by a cross-cut test according to JIS K5400. Specifically, eleven cuts were made vertically and horizontally on the surface where the gas barrier film was formed, and 100 1 mm square grids were made. A cellophane tape was applied on top of this and peeled off quickly at an angle of 90 degrees. The presence or absence was visually evaluated as follows.

◎: Not peeled off at all ○: Slight float is observed on some grids, but good quality △: Peeling is observed on 1 and 2 grids, but acceptable quality for practical use ×: Peeling is observed at three or more grids, and this is a quality that is problematic in practice (Evaluation of storage stability)
After each of the produced gas barrier films was immersed in hot water at 98 ° C. for 48 hours, the adhesion was evaluated by a cross-cut test based on JIS K 5400 in the same manner as the adhesion evaluation, and described in the adhesion evaluation. The storage stability was evaluated according to the evaluation rank.

(Evaluation of UV resistance)
Each of the gas barrier films prepared above was irradiated with 1500 mW / cm ² ultraviolet rays for 96 hours with a metal halide lamp, and then the adhesion was evaluated by a cross-cut test in accordance with JIS K 5400 in the same manner as the adhesion evaluation. The preservation was evaluated according to the evaluation rank described in the property evaluation.

[Evaluation of gas barrier properties]
(Measurement of water vapor transmission rate)
As a result of measuring the water vapor transmission rate for each untreated gas barrier film and each sample prepared with the above-described storage stability and ultraviolet resistance according to the method specified in JIS K 7129B, all the samples were 0.01 g / m ^2. / Day or less.

(Measurement of oxygen permeability)
As a result of measuring the oxygen transmission rate in accordance with the method specified in JIS K 7126B for each untreated transparent gas barrier film and each sample prepared with the above-described storage stability and ultraviolet resistance, both samples were 0.01 ml / m. ² / day or less.

  Table 1 shows the results of quality evaluation among the above evaluation results.

  As is clear from the results shown in Table 1 and the gas barrier property evaluation results, the gas barrier property of the present invention in which the adhesion film, the ceramic film, and the protective film are formed using a thin film forming gas composed of the same composition. It can be seen that the film has good gas barrier properties and is superior in adhesion, storage stability and ultraviolet resistance to the comparative example.

Example 2
<< Production of resin base material for organic electroluminescence >>
Using the gas barrier films 1 to 15 produced in Example 1, the following thin films were formed thereon, and the organic electroluminescence resin substrates 1 to 15 were produced.

(Formation of film)
On the protective film of each gas barrier film produced in Example 1, a film having a concavo-convex shape was formed according to the following method.

  A thermoplastic resin (polymethyl methacrylate (n = 1.48)) was used as a material for forming the light extraction layer on the protective film of each gas barrier film, and was applied to a thickness of about 2 μm by spin coating. Thereafter, the shape was transferred by a known press method using the following glass mold provided with a plurality of circular protrusions having a period of 300 nm, a height of 100 nm, and a diameter of 150 nm. As a result, a film made of a thermoplastic resin was formed as a plurality of cylindrical depressions having a period of 300 nm, a depth of 100 nm, and a diameter of 150 nm.

(Production of glass mold)
After applying a resist on a glass substrate (quartz glass, size: 30 mm × 30 mm, thickness: 1.0 mm), a diameter having a period of 300 nm in a square lattice as a diffraction grating by using electron beam lithography and dry etching A cylindrical mold having a thickness of 100 nm from the flat portion of the glass substrate to the top of the projection was formed on the glass substrate surface at 150 nm to produce a glass mold.

(Formation of high refractive index film)
<Preparation of coating solution for high refractive index film>
First, a mixed solvent was prepared in a container at the following ratio.

Propylene glycol monomethyl ether 4900 parts by mass Isopropyl alcohol 8900 parts by mass The following were sequentially added to and mixed with this mixed solvent to obtain a high refractive index film composition.

Tetra (n) butoxytitanium 310 parts by mass Terminal reactive dimethyl silicone oil (L-9000, manufactured by Nippon Unicar Co., Ltd.)
0.4 parts by mass Aminopropyltrimethoxysilane (KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.)
4.8 parts by mass UV curable resin (manufactured by Asahi Denka Kogyo Co., Ltd .: KR-500) 4.6 parts by mass <Application of high refractive index film coating solution>
On the light extraction layer of each sample formed above, the above prepared high refractive index film coating solution was applied using an extrusion coater so that the dry film thickness was 60 nm, and then dried to form a high refractive index film. Formed. The refractive index of this high refractive index film was 2.02.

[Formation of transparent conductive film]
On the film | membrane formed as mentioned above of each sample, the transparent conductive film was formed with the following method and the resin base materials 1-15 for organic electroluminescence were produced.

  As the plasma discharge device, the electrode shown in FIG. 2 was a parallel plate type, and each sample 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 surface of the dielectric thus coated was polished and smoothed so that the Rmax was 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 JRF-10000 manufactured by JEOL 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 allowed to flow between the electrodes to form a plasma state, each of the above samples 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 film as a transparent conductive film. Filmed.

Discharge gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
<< Production of organic electroluminescence element >>
Each organic electroluminescence resin substrate on which the ITO film is formed is a substrate of 100 mm × 100 mm. After patterning, the organic electroluminescence resin substrate provided with the ITO transparent electrode is superposed with isopropyl alcohol. Sonic cleaning and drying with dry nitrogen gas. 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 elements 1-15 were produced.

<< Evaluation of organic EL elements >>
For each organic EL element produced as follows, the measurement of light emission luminance (cd / m ² ) when a 10 V DC voltage was applied under the measurement conditions of a temperature of 23 ° C. and a dry nitrogen gas atmosphere, and 10 mA / As a result of measuring the time required for the initial luminance to be reduced to half when driven at a constant current of cm ² , that is, the half-life (light emission lifetime), It was confirmed that the organic EL element had higher emission luminance and longer emission lifetime than the comparative example.

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 a schematic block diagram which shows another example of the flat electrode type atmospheric pressure plasma processing apparatus preferably used 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 resin film 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 a roll rotating electrode, 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 20 Electric field application means 21 1st power supply 22 2nd power supply 30 Plasma discharge processing chamber 25, 35 Roll electrode 36 Electrode 41, 42 Power supply 51 Gas supply apparatus 55 Electrode cooling unit F Original roll resin film

Claims (4)

In the method for producing a gas barrier film in which an adhesive film, a ceramic film, and a protective film are sequentially formed on the resin film from the resin film side, the adhesive film, the ceramic film, and the protective film are silicon oxide films, and the same composition All layers of the adhesion film, the ceramic film, and the protective film are supplied to the discharge space with a gas containing a thin film forming gas and a discharge gas under atmospheric pressure or a pressure in the vicinity thereof, and the discharge space is supplied to the discharge space. Exciting the gas by applying a high-frequency electric field, forming the thin film on the substrate by exposing the substrate to the excited gas, and forming the thin film on the substrate, the discharge gas is nitrogen gas, The high frequency electric field applied to the discharge space is a superposition of the first high frequency electric field and the second high frequency electric field, and the density of the adhesion film is 1.85 to 2.00. There is from 2.05 to 2.20, the production method of the gas barrier film density of the protective film is characterized in 1.85 to 2.00 der Rukoto. The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the strength of the discharge start electric field. The relationship with IV satisfies the relationship of V1 ≧ IV> V2 or V1> IV ≧ V2, and the output density of the second high-frequency electric field is 1 W / cm ² or more . A method for producing a gas barrier film. A refractive index for forming a film by a sol-gel reaction on a protective film of the gas barrier film produced by the method for producing a gas barrier film according to claim 1 is further provided. above, it provided 2.1 the following high-refractive index film by a wet coating method, further manufacturing how organic electroluminescence resin base material and forming a transparent conductive film thereon. On the resin substrate for organic electroluminescence manufactured by the method for manufacturing a resin substrate for organic electroluminescence according to claim 3, a phosphorescent organic electroluminescence material and a metal film serving as a cathode are provided and sealed. A method for producing an organic electroluminescence device characterized in that:

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