JP2008056967A - Gas barrier property resin base material, and organic electroluminescence device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier property resin base material having high gas barrier performance and excellent adhesiveness and bending resistance, and an organic electroluminescence device having excellent gas barrier resistance using the same. <P>SOLUTION: In the gas barrier property resin base material having a gas barrier layer with at least two ceramic layers containing silicon oxide being laminated on at least one surface of a transparent resin base material, at least one of the ceramic layers is a first ceramic layer containing silicon oxide having the modulus of elasticity of ≥5GPa and ≤20GPa, and the compressive stress in the gas barrier layer is ≥0MPa and ≤20MPa. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a gas barrier resin substrate having a ceramic layer containing laminated silicon oxide and an organic electroluminescence device formed using the gas barrier resin substrate.

  Conventionally, a gas barrier film in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles that require blocking of various gases such as water vapor and oxygen. It is widely used for packaging, etc. 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) devices, and the like. In particular, transparent substrates, which are being applied to liquid crystal display elements, organic EL devices, etc., have recently been required to be lighter and larger, have long-term reliability and a high degree of freedom in shape, and have curved display. In addition to high demand factors such as being possible, film base materials such as transparent plastics have begun to be used instead of glass substrates that are heavy and easily broken.

  In addition, the plastic film not only meets the above requirements, but also enables a roll-to-roll method, so that it is superior in productivity to a glass substrate and is advantageous from the viewpoint of economy.

  However, film substrates such as transparent plastics have a problem that gas barrier properties are inferior to substrates such as glass. When a base material with inferior gas barrier properties is used, water vapor or air permeates, for example, the liquid crystal in the liquid crystal cell is deteriorated, resulting in display defects and deterioration of display quality.

  As one method for solving such a problem, there is known a method in which a metal oxide thin film is formed on a film substrate to form a film base material having a gas barrier property.

Examples of gas barrier films used for packaging materials and liquid crystal display elements include, for example, 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, Patent Document 2). All of which have a water vapor barrier property of about 1 g / m ² / day in terms of water vapor transmission rate.

In recent years, due to the development of organic EL displays that require further gas barrier properties, larger liquid crystal displays, and high-definition displays, the demand for gas barrier performance for film substrates is 10 ⁻² g / m for water vapor barriers. It has risen to about ² / day. 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 composition of the ceramic layer and the polymer layer is generally greatly different, the adhesion at each contact interface portion may be deteriorated, which may cause. 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.

  On the other hand, a method of laminating silicon oxide having a different carbon content is disclosed as a gas barrier resin base material with little quality deterioration such as film peeling and excellent adhesion (see Patent Documents 4 and 5).

  However, even when these gas barrier resin base materials are used, when the substrate and the sealing member are bonded using an adhesive, such as when used as a substrate of a flat panel display, for example, an organic EL display, adhesion between the base materials Turned out to be insufficient.

Moreover, the gas barrier laminated film which has the laminated structure of the ceramic layer which consists of an inorganic compound is disclosed by the sealing material of an organic electroluminescent device (for example, refer patent document 6). The laminated structure of the ceramic layer made of such an inorganic compound can obtain high barrier performance with a small number of units (number of layers) compared to the laminated structure of the inorganic compound-organic compound. When a laminated structure is configured, the hardness of the gas barrier film formed is inevitably high, so that adhesion and bending resistance between the constituent layers of the gas barrier film are insufficient, and deterioration of the barrier performance due to this is a problem. It was.
Japanese Patent Publication No.53-12953 JP 58-217344 A US Pat. No. 6,268,695 JP 2003-257619 A JP-A-8-48369 JP 2003-243155 A

  Accordingly, the present invention provides a gas barrier resin base material having high gas barrier performance and excellent adhesion and bending resistance, and an organic electroluminescence device (hereinafter referred to as organic EL or OLED) having excellent gas barrier resistance using the same. Is to provide).

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

  1. In a gas barrier resin substrate having a gas barrier layer in which a ceramic layer containing at least two layers of silicon oxide is laminated on at least one surface of a transparent resin substrate, at least one of the ceramic layers has an elastic modulus of 5 GPa or more, A gas barrier resin base material, wherein the gas barrier resin base material is a first ceramic layer containing silicon oxide of 20 GPa or less, and the compression stress of the gas barrier layer is 0 MPa or more and 20 MPa or less.

  2. The first ceramic layer has a laminated structure in which a second ceramic layer containing silicon oxide is formed on the first ceramic layer, and the second ceramic layer has an elastic modulus E1 with respect to the elastic modulus E1. 2. The gas barrier resin substrate according to 1 above, wherein the ceramic layer has an elastic modulus E2 ratio (E2 / E1) of 1.0 or more and 10.0 or less.

  3. 3. The gas barrier resin substrate according to 1 or 2 above, wherein the carbon content of the first ceramic layer is 0.2% or more and 4.9% or less in terms of atomic number concentration.

  4). 4. The gas barrier resin substrate according to any one of 1 to 3, wherein the film density of the first ceramic layer is 1.80 or more and 2.15 or less.

  5. 5. The gas barrier resin substrate according to any one of 1 to 4, wherein the first ceramic layer is formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied.

  6). 6. The gas barrier resin substrate according to any one of 1 to 5, wherein the carbon content of the second ceramic layer is 0.1% or less in terms of atomic number concentration.

  7). 7. The gas barrier resin substrate according to any one of 1 to 6, wherein the film density of the second ceramic layer is 2.15 or more and 2.50 or less.

  8). 8. The gas barrier resin substrate according to any one of 1 to 7, wherein the second ceramic layer is formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied.

9. 9. The gas barrier resin group as described in any one of 1 to 8 above, wherein the water vapor permeability is 1 × 10 ⁻⁷ g / m ² / day or more and less than 0.01 g / m ² / day. Wood.

  10. On the gas barrier resin substrate according to any one of 1 to 9, at least an electrode and an organic compound layer are formed, and a sealing member is disposed so as to cover the electrode and the organic compound layer, An organic electroluminescence device, wherein the sealing member and the gas barrier resin base material are bonded and sealed.

  11. 10. The organic electroluminescent device according to 10, wherein the sealing member is the gas barrier resin base material according to any one of 1 to 9.

  According to the present invention, a gas barrier resin base material having high gas barrier performance and excellent adhesion and flex resistance, and an organic electroluminescence device excellent in gas barrier resistance using the same can be provided.

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

  The laminated structure of the ceramic layer made of an inorganic compound as described in Patent Document 6 described above has a higher hardness of the formed gas barrier film than the laminated structure of the inorganic compound-organic compound. As a result, the adhesion and bending resistance of the film became insufficient, and the deterioration of the barrier performance due to it was a problem. As a result of intensive studies in view of the above problems, the present inventor, in a gas barrier resin substrate having a gas barrier layer in which a ceramic layer containing at least two layers of silicon oxide is laminated on at least one surface of a transparent resin substrate. And at least one of the ceramic layers is a first ceramic layer containing silicon oxide having an elastic modulus of 5 GPa or more and 20 GPa or less, and the compressive stress of the gas barrier layer is 0 MPa or more and 20 MPa or less. It has been found that a gas barrier resin substrate having high gas barrier performance and excellent adhesion and bending resistance can be realized by the gas barrier resin substrate.

  Details of the present invention will be described below.

  The gas barrier resin substrate of the present invention has a ceramic layer containing a plurality of silicon oxides on a transparent resin substrate, and at least one of the ceramic layers is made of silicon oxide having an elastic modulus of 5 GPa or more and 20 GPa or less. It is the 1st ceramic layer to contain, The compressive stress of this gas barrier layer is 0 Mpa or more and 20 Mpa or less, It is characterized by the above-mentioned.

  Furthermore, it has a laminated structure in which a second ceramic layer containing silicon oxide is formed on the first ceramic layer, and the elastic modulus E2 of the second ceramic layer with respect to the elastic modulus E1 of the first ceramic layer. The ratio (E2 / E1) is preferably 1.0 or more and 10.0 or less.

  The elastic modulus of the ceramic layer in the present invention can be determined by a conventionally known elastic modulus measuring method. For example, a condition for applying a constant strain at a constant frequency (Hz) using Vibron DDV-2 manufactured by Orientec Corporation. Method of measuring under the above, using RSA-II (manufactured by Rheometrics) as a measuring device, forming a ceramic layer on a transparent substrate, and then obtaining from the measured value obtained when the applied strain is changed at a constant frequency Alternatively, it can be measured by a nano indenter to which the nano indentation method is applied, for example, a nano indenter (Nano Indenter TMXP / DCM) manufactured by MTS System, but the extremely thin ceramic layer according to the present invention can be measured. From the viewpoint that the elastic modulus can be measured with high accuracy, a method of measuring and obtaining with a nanoindenter is preferable.

  The nano-indentation method applies an indentation of a triangular pyramid with a tip radius of about 0.1 to 1 μm to the ceramic layer provided on the transparent substrate that is the object to be measured. After that, the indenter is returned and unloaded, the obtained load-displacement curve is created, and the elastic modulus (Reduced modulus) is measured from the load and the indentation depth obtained from the load-displacement curve. In this nanoindentation method, it is possible to measure with a high accuracy of 0.01 nm as a displacement resolution using a head assembly having an ultra-low load, for example, a maximum load of 20 mN and a load resolution of 1 nN.

  Also, for laminated ceramic layers, it is possible to measure the elastic modulus of each layer by pushing an indenter with a very small triangular pyramid from the cross section. Nanoindenters that operate in electron microscopes have also been developed and can be determined by applying them.

  In the present invention, the method for forming the first ceramic layer having the elastic modulus defined in the present invention is not particularly limited, but atmospheric pressure plasma that applies two or more electric fields having different frequencies according to the present invention described later. In the case of forming by the method, the carbon content concentration or the film density of the ceramic film is appropriately adjusted by controlling the output of the power source to be applied or by controlling the concentration of supplying the raw material during the atmospheric pressure plasma treatment. Thus, a desired elastic modulus can be achieved. Specifically, the elastic modulus can be reduced by increasing the power output during the atmospheric pressure plasma treatment or by lowering the supply concentration of the raw material during the atmospheric pressure plasma treatment. Can be high.

  The compressive stress referred to in the present invention is a stress generated inside the formed gas barrier film, and in the case of compressive stress, the gas barrier film formed on the transparent resin substrate shrinks relative to the substrate. Is expressed as a positive internal stress, and conversely, when a negative curl is generated by a tensile stress, it is expressed as a negative internal stress (tensile stress).

  The internal stress in the gas barrier film composed of the ceramic layer can be measured by the following method.

  A gas barrier film having the same composition, configuration, and thickness as the gas barrier film to be measured was formed on a quartz substrate having a width of 10 mm, a length of 50 mm, and a thickness of 0.1 mm so as to have a thickness of 1 μm according to the same formation method. The resulting curl can be determined by measuring with a thin film property evaluation apparatus MH4000 manufactured by NEC Sanei Co., Ltd. with the concave portion of the sample facing upward.

  In general, in the case of a film having a low internal stress, since the internal strain is small, it means that it is smooth and average strong against deformation due to bending or the like, so that the compressive stress of the gas barrier layer which is a thin film according to the present invention. Is characterized by being 0 MPa or more and 20 MPa or less.

The gas barrier film according to the present invention is usually a film having a dense structure and a dense structure formed so as to have a water vapor transmission coefficient of 1.0 × 10 ⁻³ (g / m ² / day) or less. Since it is a film sensitive to bending and cracking, it is a film with a low internal stress having a low compressive stress of 0 MPa or more and 20 MPa or less. When the internal stress is too large, it is particularly sensitive to breakage and cracking, and sufficient attention is required in manufacturing and further processing of a ceramic film using the same, and the yield of the process is low. On the other hand, if it is too small, there may be a partial tensile stress. Similarly, the film is easily cracked or cracked, resulting in a non-durable film.

  In the present invention, the method for achieving the compressive stress of the gas barrier film defined in the present invention is not particularly limited. For example, the ceramic layer having the elastic modulus defined in the present invention, or the elastic modulus ratio defined in the present invention. By using the ceramic layer group consisting of the above, the target compressive stress can be obtained.

  In the gas barrier resin substrate of the present invention, the first ceramic layer according to the present invention formed on the transparent resin substrate has a carbon content of 0.2% or more and 4.9% or less in terms of atomic number concentration. It is preferable that the film density is 1.80 or more and 2.15 or less. The second ceramic layer formed on the first ceramic layer has a carbon content of 0.1% or less in terms of atomic number, or a film density of 2.15 or more and 2.50. The following is preferable. In addition, the first ceramic layer or the second ceramic layer according to the present invention may be formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied, from the viewpoint of further achieving the object effect of the present invention. preferable.

  In the first ceramic layer or the second ceramic layer according to the present invention, as a means for achieving the carbon content or the film density defined in the present invention, for example, when the ceramic layer is formed by an atmospheric pressure plasma method It can be obtained by controlling the output of the power source applied to the counter electrode or the raw material gas concentration in the thin film forming gas supplied to the discharge space.

  In the present invention, by providing the first ceramic layer having a relatively high carbon content and a low film density on the transparent resin substrate side, it is possible to impart good film flexibility and bending. It has properties as a stress relaxation layer against tension and tension, and at the same time, excellent adhesiveness (also referred to as adhesion) between transparent resin substrates can be obtained. However, since this first ceramic layer alone is somewhat insufficient as a gas barrier performance, it has a relatively low carbon content on the first ceramic layer, and has a high film density and excellent gas barrier properties against water vapor, oxygen, etc. By providing the second ceramic layer provided with the above, it is flexible and has a high gas barrier property, and the surface is not easily damaged, and at the same time, it adheres between the gas barrier resin base materials of the present invention and other gas barrier films. In some cases, a gas barrier resin base material that has good adhesion and is difficult to peel off even after adhesion and has greatly improved adhesion between resin base materials can be obtained.

  In the gas barrier resin substrate of the present invention, the second ceramic layer may have a distribution of film density or carbon content in the thickness direction. Each of the first ceramic layer and the second ceramic layer according to the present invention may be a single layer or a unit composed of a plurality of layers. Moreover, the unit comprised from a 1st ceramic layer and a 2nd ceramic layer may be the structure which laminated | stacked the single unit or several units.

  The carbon content in the ceramic layer referred to in the present invention is expressed in atomic concentration% (atomic concentration) of carbon atoms.

  The atomic number concentration% in the ceramic layer can be determined using a known analysis means, but in the present invention, it is calculated by the following XPS method and is defined below.

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

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

  Next, with respect to all the detected elements except for the etching ion species, the data acquisition interval is set to 0.2 eV, and the photoelectron peak giving the maximum intensity is narrow-scanned, and the spectrum of each element is 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, processing is performed with the same software, and the value of the content of the analysis target element (carbon, oxygen, silicon, etc.) is obtained as the atomic concentration (at%).

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

  The first and second ceramic layers according to the present invention are preferably films containing the same composition and having different densities. This is because even if the same composition is used, when a thin film is formed using a vapor phase growth method, for example, in the case of the atmospheric pressure plasma method, the manufacturing conditions and the thin film forming gas used (source gas, additive gas, etc.) Depending on the type, ratio, etc., the degree of filling of silicon oxide particles and the difference in the amount of mixed impurity particles, etc., the physical properties associated therewith, such as density, differ.

  As described above, the first ceramic layer of the present invention is preferably a film having a film density of 1.80 or more and 2.05 or less, and the second ceramic layer is 2.15 or more and 2.50. It is preferable to have the following film density.

  In the present invention, for these film densities, values obtained by the X-ray reflectivity method shown below are 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.

  This is a method in which X-rays are incident on a material having a flat surface at a very shallow angle, and 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. From each parameter, the thickness and density of the laminated film can be obtained. The film thickness evaluation of the laminated film in the present invention can also be obtained from the X-ray reflectivity measurement.

  The density of the ceramic layer is closely correlated with the carbon content. For example, the second ceramic layer having a high gas barrier property is a film having a low carbon atom concentration, but the density is high. The ceramic layer is a film having a higher carbon atom concentration, a softer composition, and a lower film density.

  These gas barrier layers according to the present invention can be formed by using physical vapor deposition or chemical vapor deposition.

  In addition, when physical vapor deposition or chemical vapor deposition is used, the first and second ceramic layers are sequentially formed on the resin substrate only by changing the film raw material and its conditions. The film can be formed and can be formed continuously using the same manufacturing method.

  The physical vapor deposition method is a method in which a thin film of a target substance (in this case, silicon oxide) is deposited on the surface of the substance in a gas phase by a physical method, and these methods include vapor deposition (resistance heating method). , Electron beam evaporation, molecular beam epitaxy) method, ion plating method, sputtering method, etc., and any method can be used. Among these methods, sputtering method that can be easily applied to high melting point materials. Are preferable for forming a ceramic layer containing silicon oxide.

  The chemical vapor deposition method is a method in which a source gas containing a target thin film component is supplied onto a substrate material, and a film is deposited by a chemical reaction on the surface of the substrate or in the gas phase. There is a method of generating plasma or the like for the purpose of activating.

  As these chemical vapor deposition methods, there are a thermal CVD method and a plasma CVD (vacuum, atmospheric pressure) method that can easily form different ceramic layers by changing and adjusting the source gas. The atmospheric pressure plasma method having a high film formation rate is a particularly preferable method.

  Among the atmospheric pressure plasma methods, a so-called two-frequency atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied is particularly preferable, which will be described in detail later.

  Therefore, it is particularly preferable that the first ceramic layer and the second ceramic layer are formed by using an atmospheric pressure plasma method, particularly a two-frequency atmospheric pressure plasma method.

In this way, the vapor phase growth method, particularly the atmospheric pressure plasma method is used to sequentially contain silicon oxide having a carbon content of 0.2 to 4.9% in terms of atomic number concentration on the transparent resin substrate. One ceramic layer and a second ceramic layer containing silicon oxide having a carbon content of 0.1% or less in terms of atomic concentration are sequentially formed, and a set of gas barrier thin film laminates composed of these layers is formed. The gas barrier resin base material formed by at least one set has a water vapor transmission rate of at least less than 0.01 g / m ² / day and 1 × 10 ⁻⁷ g / m ² / day or more. In this case, a gas barrier resin substrate having excellent adhesiveness can be obtained.

In the present invention, the water vapor transmission rate is measured by the method described in JIS K 7129B. For measurement, a water vapor transmission rate measuring device PERMATRAN-W 3/33 MG module manufactured by MOCON can be used [g / m ² / day].

Similarly, oxygen permeability can be measured using an oxygen permeability measuring device OX-TRAN 2/21 ML module manufactured by MOCON according to JIS K 7126B [cm ³ / m ² / day / atm]. .

  The thickness of the gas barrier layer laminate composed of ceramic layers having different carbon contents according to the present invention is appropriately selected depending on the type and configuration of the material used, and may be within a range of 1 to 5000 nm. More preferably, it is in the range of 5 to 500 nm. This is because if the thickness of the gas barrier thin film laminate is thinner than the above range, a uniform film cannot be obtained, and it is difficult to obtain a gas barrier property. In particular, the thickness of the second ceramic layer is preferably in the range of 1 to 5000 nm, more preferably in the range of 5 to 500 nm. When the second ceramic layer is thicker than the above range, it is difficult to maintain the flexibility of the resin base material (film). Due to external factors such as bending and pulling after film formation, the gas barrier resin base This is because cracks may occur in the material.

  In the configuration of the present invention, the first ceramic layer is a layer having a role of stress relaxation. However, when the first ceramic layer is also used as an adhesion film for improving adhesion between the base material and the second ceramic layer, the first ceramic layer has a thickness of 1 to 500 nm. More preferably, it is 20-200 nm.

  In the present invention, the gas barrier layer comprising the first and second ceramic layers containing silicon oxide can be formed by a physical or chemical vapor deposition method using a silicon compound as a raw material. It is preferable to form on a transparent resin base material using an atmospheric pressure plasma method.

  First, in the method for producing the first and second ceramic layers according to the present invention, the raw material compounds used in the production method by the atmospheric pressure plasma method will be described.

  The ceramic layer according to the present invention is mainly composed of silicon oxide or silicon oxide by selecting conditions such as an organometallic compound, decomposition gas, decomposition temperature, input power and the like as raw materials (also referred to as raw materials) in the atmospheric pressure plasma method. In addition, the composition of the metal oxide, metal carbide, metal nitride, metal sulfide, metal halide and the like (metal oxynitride, metal oxide halide, etc.) can be made separately.

  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. Further, if silazane or the like is used as a raw material compound, silicon oxynitride 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 a raw material for forming such a ceramic layer, as long as it is a silicon compound, 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.

  Examples of such silicon compounds include 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 (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethyl Aminotrimethylsilane, 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, propa Gil trimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclo Examples thereof include tetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  The decomposition gas for decomposing the raw material gas containing silicon to obtain the ceramic layer includes hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, and nitrous oxide gas. , Nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas and the like.

  By appropriately selecting a source gas containing silicon and a decomposition gas, a ceramic layer containing silicon oxide, nitride, carbide, or the like can be obtained.

  In the atmospheric pressure plasma method, a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases, and the gas is sent to a 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 supplied to an atmospheric pressure plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. 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 laminated ceramic layer constituting the gas barrier resin base material of the present invention, for example, the above-mentioned organosilicon compound is further combined with oxygen gas or nitrogen gas at a predetermined ratio, and at least one of O atom and N atom, A ceramic layer mainly containing silicon oxide according to the present invention containing Si atoms can be obtained.

  (1) and (2) in FIG. 1 are cross-sectional views showing a layer configuration example of a gas barrier resin substrate according to the present invention. As the resin substrate, for example, a PET (polyethylene terephthalate) film is used, and in FIG. 1, the polymer layer described later has a smoothness, a unit composed of the first and second ceramic layers according to the present invention, and a resin group. It is formed to improve adhesion to the material (film) and to ensure smoothness. Further, a third ceramic layer may be further formed as a protective film.

(1) Resin substrate 1 (125 μm) / polymer layer 2 (6 μm) / first ceramic layer 3 (100 nm) / second ceramic layer 4 (50 nm) / third ceramic layer 5 (500 nm)
(2) Resin substrate 1 / polymer layer 2 / first ceramic layer 3 (100 nm) / second ceramic layer 4 (50 nm) / first ceramic layer 5 (100 nm) / second ceramic layer 4 (50 nm ) / Third ceramic layer 5 (100 nm)
In the above, () indicates the thickness of each film. In addition, the third ceramic layer (film) which is the outermost surface layer in each of them also serves as a protective film. The polymer layer has a role of further improving the adhesion between the first ceramic layer (film) and the substrate.

  In the present invention, the polymer layer provided between the first ceramic layer 3 and the resin base material (resin film base material to be described later) is preferably a resin coat layer such as an acrylic resin, a polyester resin, or a urethane resin. It can be easily formed by coating a corresponding resin solution on a resin substrate by a known method such as gravure coating or dip coating.

  In the present invention, these polymer layers are preferably formed from a thermosetting resin or an actinic radiation curable resin, and it is particularly preferable to form a cured resin layer using an ultraviolet curable resin. In addition, before forming these layers, it is preferable that the surface of the resin base material (film) is subjected to corona discharge treatment or glow discharge treatment.

  The cured resin layer is preferably a layer formed by polymerizing a component containing at least one monomer having an ethylenically unsaturated bond, and a resin formed by polymerizing a component containing a monomer having an ethylenically unsaturated bond As the layer, a layer formed by curing an actinic ray curable resin or a thermosetting resin is preferably used, and an actinic ray curable resin layer is particularly preferably used. Here, the actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams.

  Typical examples of the actinic radiation curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may also be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. For example, an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin, which are mainly composed of acrylic, are preferable.

  Specific examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like.

  In general, UV-curable acrylic urethane resins include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. And acrylate-based monomers such as 2-hydroxypropyl acrylate, which are easily formed by reaction with acrylate monomers having hydroxyl groups, such as those described in JP-A-59-151110. Can be used.

  Examples of UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as disclosed in JP-A-59-151112. Those described can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.

  Specific examples of these photoinitiators include benzoin and derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoreactive agent, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available UV curable resins that can be used in the present invention include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, Asahi) Manufactured by Denka Co., Ltd.); Koei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102 NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (above, manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3) , PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, large Manufactured by Seika Kogyo Co., Ltd.); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC -5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601 (manufactured by Sanyo Chemical Industries); SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.); RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) and the like can be appropriately selected and used.

  These actinic radiation curable resin layers can be applied by a known method.

As a light source for curing the ultraviolet curable resin by a photocuring reaction, any light source that generates ultraviolet light can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. By using a sensitizer having an absorption maximum in the near-ultraviolet region to the visible light region, it can be efficiently formed.

  The organic solvent for the UV curable resin layer composition coating solution is appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other organic solvents, or mixed and used. it can. For example, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5%. It is preferable to use the organic solvent containing -80% by mass or more.

  The coating amount of the ultraviolet curable resin composition coating solution is suitably from 0.1 to 30 μm, preferably from 0.5 to 15 μm, as the wet film thickness. The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds from the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin. More preferred is ~ 2 minutes.

  Further, as the polymer film according to the present invention, a plasma polymerization film formed by using an atmospheric pressure plasma method which is a chemical vapor deposition method is also preferable. That is, it is possible to form a polymer film by plasma-polymerizing an organic compound by containing at least one organic compound in a thin film forming gas using an atmospheric pressure plasma method.

  As an organic compound which is a raw material component of plasma polymerization using the atmospheric pressure plasma method, a known organic compound can be used, and among them, an organic compound having at least one unsaturated bond or cyclic structure in the molecule. A compound can be preferably used, and in particular, a monomer or oligomer of a (meth) acryl compound, an epoxy compound, or an oxetane compound can be preferably used. To do.

  Although there is no limitation in particular as a useful (meth) acryl compound, The following compounds are mention | raise | lifted as a typical example. 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3-dioxane alcohol Of ε-caprolactone adduct, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or methacrylic acid esters obtained by replacing these acrylates with methacrylates, such as ethylene glycol diacrylate, triethylene glycol diacrylate , Pentaerythritol diacrylate, hydroquinone diacrylate, resorcindiak Rate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of neopentyl glycol adipate, ε-caprolactone adduct of neopentyl glycol hydroxypivalate Ε of diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate -Bifunctional acrylic acid esters such as caprolactone adduct, diglycidyl ether diacrylate of 1,6-hexanediol, or these acrylates Methacrylic acid esters instead of relate, such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, etc. The polyfunctional acrylic acid Ester acid or methacrylic acid or the like instead of these acrylate with methacrylate. The compounds mentioned as the actinic radiation curable resin are also included.

  The discharge gas is the same as in the case of forming the ceramic layer, and includes nitrogen, rare gas, air, etc. As the rare gas, the 18th group element of the periodic table, specifically, helium, neon, argon, It is selected from krypton, xenon, radon and the like, and in the present invention, the discharge gas is preferably nitrogen, argon or helium, more preferably nitrogen.

  In the plasma polymerization, the discharge gas amount is preferably 70 to 99.99% by volume with respect to the thin film forming gas amount supplied into the discharge space.

  Also in the plasma polymerization method, in addition to the raw material gas and discharge gas, an additive gas may be introduced to control the reaction and film quality, and hydrocarbons such as hydrogen, oxygen, nitrogen oxides, ammonia, methane, etc. Alcohols, organic acids, or moisture may be mixed in 0.001% to 30% by volume with respect to the gas.

  Subsequently, the resin film which is a transparent resin base material concerning this invention is demonstrated.

  The transparent resin base material (hereinafter also referred to as a resin film) used in the gas barrier resin base material of the present invention is not particularly limited as long as it is a resin film that can hold the above-described gas barrier layer.

  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 resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA), and the like 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), cellulose triacetate film Konica Minolta Commercial products such as Tuck 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. Therefore, an organic electroluminescence element (hereinafter abbreviated as an organic EL element) This is because a transparent substrate such as can be used.

  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.

  Further, in the resin film substrate according to the present invention, surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc. before forming the gas barrier film or polymer film, etc. May be performed.

  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 due to its suitability as a packaging material. 3 to 400 [mu] m, preferably 6 to 30 [mu] m.

  Moreover, as for the film thickness of the resin film used for this invention, 10-200 micrometers is preferable, More preferably, it is 50-200100 micrometers.

As the water vapor permeability of the gas barrier resin substrate of the present invention, the water vapor permeability measured according to the JIS K7129 B method when used for applications requiring high water vapor barrier properties such as organic EL displays and high-definition color liquid crystal displays. Is not more than 0.01 g / m ² / day, more preferably not more than 1 × 10 ⁻³ g / m ² / day, and in the case of organic EL display applications, even if it is extremely small, it grows dark Since spots may occur and the display life of the display may become extremely short, the water vapor transmission rate is preferably less than 1 × 10 ⁻⁵ g / m ² / day.

  Next, the atmospheric pressure plasma method according to the present invention will be described.

  A physical or chemical vapor deposition method is used to form a buffer film or a barrier film made of a ceramic layer according to the present invention, or a laminate thereof. Among these, the atmospheric pressure plasma method, which is the most preferable method among these, will be described below.

  The atmospheric pressure plasma method is described in, for example, Japanese Patent Application Laid-Open No. 10-154598, Japanese Patent Application Laid-Open No. 2003-49272, International Publication No. 02/048428, and the like. The described thin film forming method is preferable for forming a dense ceramic layer having a high gas barrier property. Moreover, a web-like base material is drawn out from a roll-shaped original winding, and ceramic layers having different compositions can be continuously formed.

  The above atmospheric pressure plasma method according to the present invention is a plasma CVD method performed under atmospheric pressure or a pressure in the vicinity thereof, and the atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa, and is described in the present invention. In order to obtain a good effect, 93 kPa to 104 kPa is preferable.

  The discharge condition in the present invention is preferably such that two or more electric fields having different frequencies are applied to the discharge space, and the electric field is applied by superimposing the first high-frequency electric field and the second high-frequency electric field.

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 discharge start The relationship with the electric field strength IV is
V1 ≧ IV> V2
Or V1> IV ≧ V2 is satisfied,
The power density of the second high frequency electric field is 1 W / cm ² or more.

  High frequency refers to one having a frequency of at least 0.5 kHz.

  When the superposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform is a sine of the frequency ω1. A sawtooth waveform in which a sine wave having a higher frequency ω2 is superimposed on the wave is obtained.

  In the present invention, the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (such as electrode configuration) and reaction conditions (such as gas conditions) used in the actual thin film formation method. Point to. The discharge start electric field strength varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.

  By applying a high-frequency electric field as described above to the discharge space, it is presumed that a discharge capable of forming a thin film is generated and high-density plasma necessary for forming a high-quality thin film can be generated.

  What is important here is that such a high-frequency electric field is applied between the opposing electrodes, that is, applied to the same discharge space. As disclosed in JP-A-11-16696, a method in which two application electrodes are juxtaposed and different high-frequency electric fields are applied to different discharge spaces is not preferable.

  Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves may be used, one of them may be a continuous wave and the other may be a pulse wave. Further, a third electric field having a different frequency may be included.

  As a specific method for applying the high-frequency electric field of the present invention to the same discharge space, for example, the first high-frequency electric field having the frequency ω1 and the electric field strength V1 is applied to the first electrode constituting the counter electrode. An atmospheric pressure plasma discharge processing apparatus in which a first power source is connected and a second power source for applying a second high-frequency electric field having a frequency ω2 and an electric field strength V2 is connected to the second electrode is used.

  The atmospheric pressure plasma discharge treatment apparatus includes a gas supply unit that supplies a discharge gas and a thin film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

  Further, it is preferable to connect the first filter to the first electrode, the first power source or any of them, and connect the second filter to the second electrode, the second power source or any of them, The first filter facilitates the passage of the first high-frequency electric field current from the first power source to the first electrode, grounds the second high-frequency electric field current, and the second filter from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. A power supply having a function of making it difficult to pass the current of the first high-frequency electric field to the power supply is used. Here, being difficult to pass means that it preferably passes only 20% or less, more preferably 10% or less of the current. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

  For example, as the first filter, a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several μH can be used depending on the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

  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 electric field strength than the second power source.

  Here, the applied electric field strength and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of applied electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode portion, and an output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV. The measuring instrument is the same as the applied electric field strength measurement.

  In addition, the measurement position of the electric field strength by the high frequency voltage probe and oscilloscope used for the measurement is shown in FIG.

  By adopting the discharge conditions specified in the present invention, even a discharge gas having a high discharge starting electric field strength, such as nitrogen gas, can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. Can be done.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. 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 high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is an important point of the present invention to form a dense and high-quality thin film by increasing the plasma density with a high power density.

  Also, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film formation speed and an improvement in film quality can be achieved.

  As described above, the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and places the gas between the counter electrodes or between the electrodes. By exposing the substrate to be transferred to the plasma state gas, a thin film is formed on the substrate. As another method, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or jets the gas outside the counter electrode. There is a jet type apparatus that blows out a plasma gas and exposes a substrate (which may be stationary or transferred) in the vicinity of the counter electrode to form a thin film on the substrate. .

  FIG. 2 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 application 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 <b> 1 from the first power supply 21 is output from the first electrode 11 between the counter electrodes. A first high-frequency electric field of electric field strength V1 and current I1 is applied, and a second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 from the second power source 22 is applied from the second electrode 12. It has become. The first power source 21 applies a higher frequency electric field strength (V1> V2) than the second power source 22, and the first frequency ω1 of the first power source 21 applies a frequency lower than the second frequency ω2 of the second power source 22. To do.

  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.

  The above-described thin film forming gas G is introduced from the gas supply means as shown in FIG. The second power source 22 applies the above-described high-frequency electric field between the first electrode 11 and the second electrode 12 to generate a discharge, and the thin film forming gas G described above is brought into a plasma state while the lower side of the counter electrode (below the paper surface). The processing space formed by the lower surface of the counter electrode and the base material F is filled with a gas G ° in a plasma state, and is unwound from a base winding (unwinder) (not shown). A thin film is formed in the vicinity of the processing position 14 on the base material F that is transported or transported from the previous process. During the thin film formation, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the base material during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that temperature unevenness in the width direction or longitudinal direction of the substrate does not occur as much as possible.

  FIG. 2 shows a measuring instrument and a measurement position used for measuring the applied electric field strength and the discharge starting electric field strength. Reference numerals 25 and 26 are high-frequency voltage probes, and reference numerals 27 and 28 are oscilloscopes.

  By arranging a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses in parallel with the transport direction of the base material F and simultaneously discharging gas in the same plasma state, it becomes possible to form a plurality of thin films at the same position, and for a short time. Thus, a desired film thickness can be formed. If a plurality of units are arranged in parallel with the conveying direction of the base material F, different thin film forming gases are supplied to each apparatus and different plasma state gases are jetted, it is also possible to form laminated thin films having different layers.

  FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus that treats a substrate between counter electrodes useful for the present invention.

  The atmospheric pressure plasma discharge treatment apparatus of the present invention is an apparatus having at least a plasma discharge treatment apparatus 30, an electric field application means 40 having two power supplies, a gas supply means 50, and an electrode temperature adjustment means 60.

  Between the counter electrodes 32 (hereinafter referred to as discharge between the counter electrodes) between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36 (hereinafter, the square tube type fixed electrode group is referred to as a fixed electrode group). In this case, the base material F is plasma-discharged to form a thin film.

  In the discharge space 32 formed between the roll rotating electrode 35 and the fixed electrode group 36, the roll rotating electrode 35 receives a first high-frequency electric field of frequency ω1, electric field strength V1, current I1 from the first power source 41, and A second high-frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 is applied to the fixed electrode group 36 from the second power source 42.

  A first filter 43 is installed between the roll rotation electrode 35 and the first power supply 41. The first filter 43 facilitates the passage of current from the first power supply 41 to the first electrode, and the second power supply. It is designed to ground the current from 42 and make it difficult to pass the current from the second power source 42 to the first power source. In addition, a second filter 44 is installed between the fixed electrode group 36 and the second power source 42, and the second filter 44 facilitates passage of current from the second power source 42 to the second electrode, It is designed to ground the current from the first power supply 41 and make it difficult to pass the current from the first power supply 41 to the second power supply.

  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 source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. Current I1 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} . Furthermore, current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The thin film forming gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge processing vessel 31 from the air supply port 52 while the flow rate is controlled by a gas flow rate adjusting means (not shown).

  The substrate F is unwound from the original winding (not shown) and conveyed, or is conveyed in the direction of the arrow from the previous process and is accompanied by the nip roll 65 through the guide roll 64 and the substrate. And the like, and while being wound while being in contact with the roll rotating electrode 35, it is transferred to and from the rectangular tube fixed electrode group 36.

  An electric field is applied from both the roll rotating electrode 35 and the fixed electrode group 36 during the transfer, and discharge plasma is generated between the counter electrodes (discharge space) 32. The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35.

  A plurality of rectangular tube-shaped fixed electrodes are provided along a circumference larger than the circumference of the roll electrode, and the discharge areas of the electrodes are all the corners facing the roll rotating electrode 35. It is represented by the sum of the areas of the surface of the cylindrical fixed electrode facing the roll rotation electrode 35.

  The base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.

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

  During the thin film formation, in order to heat or cool the roll rotating electrode 35 and the fixed electrode group 36, the medium whose temperature is adjusted by the electrode temperature adjusting means 60 is sent to both electrodes via the pipe 61 by the liquid feed pump P, and inside the electrodes Adjust the temperature from 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 and to keep the surface temperature of the substrate F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) 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.

  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 performing 0.15 mm, 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. 1, it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with an object made of the above material.

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

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

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

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

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

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

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

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

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

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

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

  The metallic base material of the electrode useful in the present invention is a titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very little iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium metals have a thermal expansion coefficient that is about 1/2 smaller than that of stainless steel, such as AISI 316, and are combined with a dielectric described later applied on the titanium alloy or titanium metal as a metallic base material. It can withstand the use at high temperature for a long time.

  On the other hand, as a required characteristic of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and examples of such a dielectric include ceramics such as alumina and silicon nitride, Alternatively, there are glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  Alternatively, as one of the specifications that can withstand high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is. The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved because the dielectric has a low porosity. Examples of the dielectric having such a void and a low void ratio include a high-density, high-adhesion ceramic spray coating by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire, or the like is put into a plasma heat source and sprayed onto a metallic base material to be coated as fine particles in a molten or semi-molten state to form a film. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. The plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, high adhesion strength and high density coating can be obtained. For details, a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655 can be referred to. By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

  Another preferable specification that can withstand high power is that the dielectric thickness is 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

  In order to further reduce the porosity of the dielectric, it is preferable to further perform a sealing treatment with an inorganic compound on the sprayed film such as ceramics as described above. As the inorganic compound, a metal oxide is preferable, and among these, a compound containing silicon oxide (SiOx) as a main component is particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are sequentially repeated several times, mineralization is further improved and a dense electrode without deterioration can be obtained.

  In the case of performing a sealing treatment that cures by a sol-gel reaction after coating a ceramic sprayed film using the metal alkoxide or the like of the dielectric-coated electrode according to the present invention as a sealing liquid, the content of the metal oxide after curing is 60 It is preferably at least mol%. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the cured SiOx content (x is 2 or less) is preferably 60 mol% or more. The SiOx content after curing is measured by analyzing the tomographic layer of the dielectric layer by XPS (X-ray photoelectron spectroscopy).

  In the present invention, in the electrode according to the thin film forming method, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the base material of the electrode may be adjusted to be 10 μm or less. From the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less. In this way, the dielectric surface of the dielectric-coated electrode can be polished and the dielectric thickness and the gap between the electrodes can be kept constant, the discharge state can be stabilized, the heat shrinkage difference and Distortion and cracking due to residual stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish of the dielectric surface is preferably performed at least on the dielectric in contact with the substrate. Furthermore, the centerline average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

  In the dielectric-coated electrode used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such heat-resistant temperature can be applied within the range of the difference between the linear thermal expansion coefficient of the metallic base material and the dielectric material by applying the dielectric material provided by the above-mentioned ceramic spraying or layered glass lining with different bubble mixing amounts. This can be achieved by appropriately combining means for appropriately selecting the materials.

  In sealing an electronic device formed on a substrate, an adhesive or the like is used in some form, and the gas barrier resin base material serving as the substrate and another sealing material are bonded or adhered. For example, when used for sealing an organic EL element, the gas barrier resin substrate of the present invention is used as a substrate of the organic EL element, and another sealing material (although the gas barrier resin substrate of the present invention may be used) and A sealing structure is formed by adhering to block the element from the outside air. The gas barrier resin substrate of the present invention is characterized by good adhesion to an adhesive and less peeling between the bonded substrates.

  As long as the gas barrier resin base material of the present invention is not contrary to the gist of the present invention, an adhesive generally used for glass, plastic substrates and the like can be used without limitation.

  Examples of adhesives include photo-curing and thermosetting acrylic adhesives having reactive vinyl groups, such as polyvinyl acetate adhesives, acrylic acid oligomers, and methacrylic acid oligomers, epoxy resin adhesives, and 2-cyanoacrylic. Moisture curable adhesives such as acid esters, ethylene copolymer adhesives, polyester adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenol resin adhesives, polyurethane -Based adhesives, reactive (meth) acrylic adhesives, rubber-based adhesives, etc., and the effects thereof can be exhibited. Particularly preferred adhesives include acrylic adhesives and epoxy adhesives. Etc. can be mentioned. Among them, an epoxy adhesive having a small shrinkage upon curing is preferable.

  As an epoxy adhesive, specifically, for example, an epoxy resin composition comprising a combination of an epoxy resin and a mercaptan hardener as disclosed in JP-A-63-63716 to obtain curability at low temperatures Products, epoxy resin compositions composed of a combination with a heterocyclic diamine curing agent, and epoxy resins composed of a combination with an aromatic polyamine curing agent in order to obtain high strength. (C) polyamidoamine, (D) aromatic modified amine, and bisphenol-type epoxy resin and amine-based curing agent as disclosed in JP-A-10-120564 in order to obtain adhesion and adhesion stability with (E) Epoxy resin composition in combination with aliphatic modified polyamine, and epoxy described in JP-A-2000-229927 Curing speed which consist of a combination of fat and amine imide curing agent is fast epoxy resin composition and the like. In addition, JP-A-6-87190 and JP-A-5-295272 disclose an epoxy resin composition using a specially modified silicone prepolymer as a curing agent.

  Both are epoxy resin compositions consisting of an epoxy resin as the main agent and a curing agent. A compound containing the epoxy group (main agent) and a curing agent containing amines or acid anhydrides are mixed together and cured. An adhesive that adheres.

  As described above, the epoxy group-containing compound includes bisphenol A type, hydrogenated bisphenol A type, novolak type, bisphenol F type, brominated epoxy resin, cycloaliphatic epoxy resin, glycidylamine resin, glycidyl ester. In addition, as described above, as the curing agent, aliphatic primary and secondary amines (triethylenetetramine, dipropyltriamine, etc.), aliphatic tertiary amines (triethanolamine, aliphatic primary amines) Reaction products of 1 and secondary amines and epoxy), aliphatic polyamines (diethylenetriamine, tetraethylenepentamine, bis (hexamethylene) triamine, etc.), aromatic amines (metaphenylenediamine, diaminodiphenylmethane, diaminophenylsulfone, etc.) , Amine adduct (polyamine and epoxide Reaction products of shea group), an aromatic acid anhydride (trimellitic anhydride, pyromellitic anhydride), dicyandiamide and derivatives thereof, imidazoles or the like is used.

  As these epoxy adhesives, there are one-pack type and two-pack type adhesives, and two-pack type epoxy adhesives generally include an epoxy group-containing compound (main agent), amines, An adhesive that is mixed with a curing agent containing an acid anhydride and bonded by a curing reaction.

  Specific examples of the epoxy adhesive that can be used in the present invention include Cemedine EP-001 manufactured by Cemedine Co., Ltd., 3950 Series, 3950, 3951, 3952, 2080 Series manufactured by Three Bond Co., Ltd., 2083. , 2086, 2087, 2230 series, 2230, 2230B, 3124C, Bond MOS series manufactured by Konishi Co., Ltd., MOS07, MOS10, ULTITE 1500 series from TOHO KASEI KOGYO Co., Ltd., ULTITE 1540, etc., Nagase ChemteX Corporation XNR5576 / 5576LV, XNR5516 / 5516HV, XNR5570, T470 / UR7116, T470 / UR7134, T470 / UR7132, T470 / UR7124E-LV, and the like.

  These adhesives can be provided on the reinforcing structure such as potting, coating, spraying, printing, etc. without limitation, for example, on the organic EL substrate. When providing by potting, it is preferable to increase the number of potting nozzles. When providing by application | coating, providing smoothly is preferable.

  These epoxy adhesives are polymerized and cured by irradiation with energy rays such as ultraviolet rays and electron beams, and heat.

  Specific examples of the acrylic adhesive include an adhesive composed of an acrylic pressure-sensitive adhesive component, an energy ray curable component, and a thermosetting adhesive component.

  Examples of the acrylic pressure-sensitive adhesive include (meth) acrylic acid ester copolymers composed of structural units derived from (meth) acrylic acid ester monomers and (meth) acrylic acid derivatives. Here, the (meth) acrylic acid ester monomer is particularly preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, ( For example, propyl (meth) acrylate and butyl (meth) acrylate are used. Examples of (meth) acrylic acid derivatives include glycidyl (meth) acrylate.

  As the acrylic pressure-sensitive adhesive as described above, a copolymer of (meth) acrylic acid or glycidyl (meth) acrylate and at least one alkyl (meth) acrylate is particularly preferable. In this case, the content of component units derived from glycidyl (meth) acrylate in the copolymer is usually 0 to 80 mol%, preferably 5 to 50 mol%. The content of component units derived from (meth) acrylic acid in the copolymer is usually 0 to 40 mol%. As the (meth) acrylic acid alkyl ester, it is preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or the like, or hydroxyethyl acrylate.

  The molecular weight of the acrylic pressure-sensitive adhesive is preferably 150,000 to 1,000,000 in terms of weight average molecular weight.

  The energy ray curable component is a compound that is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams. Specific examples of this energy beam polymerizable compound include cyclic fatty acids such as trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, and dipentaerythritol hexaacrylate. Acrylate compounds such as group skeleton-containing acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer are used. Such a compound has at least one polymerizable double bond in the molecule, and usually has a molecular weight of about 300 to 10,000.

  Generally, the energy ray curable component is preferably used at a ratio of about 50 to 150 parts by mass with respect to 100 parts by mass of the acrylic adhesive component.

  The adhesive composition as described above is cured by energy beam irradiation. Specifically, ultraviolet rays, electron beams, etc. are used as the energy rays.

  When ultraviolet rays are used as energy rays, the polymerization curing time and the amount of light irradiation can be reduced by mixing a photopolymerization initiator (for example, benzophenone). The photopolymerization initiator is preferably used at a ratio of about 0.5 to 3.0 parts by mass with respect to 100 parts by mass in total of the above components.

  In addition to the above components, it does not harden depending on energy rays, but heats such as bisphenol glycidyl type epoxy resin, o-cresol novolac type epoxy resin and phenol novolac type epoxy resin, urea resin, etc. It is preferable that 1-10 mass parts and a thermally activated latent epoxy resin hardening | curing agent are contained with respect to a curable adhesive component and a thermosetting adhesive component.

  The thermally activated latent epoxy resin curing agent is a type of curing agent that does not react with the epoxy resin at room temperature but is activated by heating at a certain temperature or more and reacts with the epoxy resin.

  The said adhesive composition is normally used in the quantity of 18-70 mass parts with respect to 100 mass parts of thermosetting adhesive components.

  These acrylic adhesives also have a one-pack type and a two-pack type. Specific examples thereof include three bond, 3003, 3027B, 3033B, 3042B, etc., and cemedine Y600, cemedine Y600, Y600H etc. are mentioned.

  Other examples of the rubber-based adhesive include, for example, natural rubber mainly composed of cis-1,4-polyisoprene, synthetic rubber mainly composed of styrene / butadiene rubber (SBR), polyisobutylene, butyl rubber, or the like, or Adhesive elastomer selected from styrene / butadiene / styrene copolymer rubber (SBS), block rubber mainly composed of styrene / isoprene / styrene copolymer rubber (SIS), etc., with liquid or solid molecular weight at room temperature Is an adhesive imparting agent such as rosin resin, terpene resin, petroleum resin, chroman indene resin, which is a thermoplastic resin of amorphous oligomer (a dimer or higher medium molecular weight polymer) of several hundred to about 10,000, And blended with softeners such as mineral oil, liquid polybutene, liquid polyisobutylene, and liquid polyacrylate. It is.

  Examples of vinyl ether adhesives include homopolymers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and copolymers with acrylates (adhesive elastomers), and in some cases, the above-described adhesion-imparting agent and softener are blended. Things.

  In addition, as the silicon-based adhesive, for example, a polymer (or adhesive elastomer) having a residual silanol group (SiOH) at the end of a polymer chain represented by high molecular weight polydimethylsiloxane or polydimethyldiphenylsiloxane and the above-mentioned adhesion There are those that contain an agent, a softener and the like.

  As the two-component adhesive, polyisocyanate compounds such as aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, and these polyvalent isocyanate compounds are used. More specific examples of the monomer and terminal isocyanate urethane prepolymer obtained by reacting these polyvalent isocyanate compounds and polyol compounds include 2,4-tolylene diisocyanate, 2,6- Contains main components such as tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, polyols, amines and acid anhydrides A two-component type, such as a urethane adhesive, that mixes with a curing agent.

  Moreover, moisture hardening type adhesives, such as 2-cyanoacrylic acid ester, can also be mentioned.

  After forming the organic EL element on the gas barrier resin base material of the present invention having the laminate of the ceramic layers, the sealing material is further covered with an inert gas so as to cover the entire organic EL element. The device can be sealed by adhering the sealing material and a gas barrier resin substrate as a substrate using the adhesive.

  As a sealing material, a known gas barrier film used for a packaging material, for example, a plastic film in which silicon oxide or aluminum oxide is vapor-deposited, a structure in which a ceramic layer and an impact relaxation polymer layer are alternately laminated. Using a metal foil laminated with a polymer film or the like as a sealing film, the organic EL element is sealed by overlapping the gas barrier resin base material on which the organic EL element is formed and adhering with an adhesive. Can be stopped.

  The sealing material only needs to be a material having a high gas barrier property. For example, a glass sealing can or the like is overlapped with a gas barrier resin base material on which an organic EL element is formed, and a region in which each layer of the organic EL element is formed. It may be adhered and sealed around

  When sealing an organic EL element, a known gas barrier film used for the packaging material or the like can be used as a sealing material, but a gas barrier film made of a laminated film of silicon oxide according to the present invention is Further, the adhesiveness is improved and the sealing material is particularly preferable.

  Among known gas barrier films, resin-laminated (polymer film) metal foil cannot be used as a gas barrier film on the light extraction side, but is a low-cost, low moisture-permeable sealing material that is intended for light extraction. When not (transparency is not required), it is preferable as a sealing film.

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

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

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

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

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

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

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

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

  After forming each layer of the organic EL element on the resin film substrate (gas barrier resin substrate) having the gas barrier thin film laminate of the present invention, an inert gas is used for sealing with the sealing material. Under the purged environment, the cathode surface can be covered with the sealing film, and the adhesive can be used for curing and adhesion.

  For curing, the adhesive exposed between the sealing material and the gas barrier resin substrate is obtained from a high-pressure mercury lamp or a halogen lamp, irradiated from the substrate side with light from the ultraviolet region to the visible region, The photocurable adhesive is cured. Moreover, when heat-bonding, it can heat in the range of 50-150 degreeC. As a result, the base material and the sealing material can be integrated.

  In the case of the gas barrier resin base material of the present invention, since it is composed of a ceramic layer, there is little absorption in the ultraviolet to blue region, so when irradiating light through a substrate and sealing, even when the irradiation amount is low enough Productivity is good because it cures.

  In the present specification, “ultraviolet region (light)” means light having a wavelength in the range of 250 nm to 400 nm, and “visible region (light)” means light having a wavelength in the range of 400 nm to 700 nm. Say light.

As the inert gas, a rare gas such as He and Ar is preferably used in addition to N ₂ , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90 to 100 volumes. % Is preferred. Preservability is improved by sealing in an environment purged with an inert gas.

  Further, for example, when sealing an organic EL element using a metal foil laminated with the resin film (polymer film) as a sealing film, the laminated resin film surface of the organic EL element is used. It can be sealed against the cathode surface.

  Further, when using a metal foil laminated with a resin film (polymer film), a ceramic film such as silicon oxide is formed on the metal foil opposite to the polymer film, and this ceramic film surface is used as a cathode of the organic EL element. It is preferable to oppose, adhere and bond. When the polymer film surface of the sealing film is bonded to the cathode of the organic EL element, conduction may be partially generated, or electrical decoration associated therewith may be generated, thereby generating a dark spot. The ceramic film formed on the metal foil is preferably silicon oxide, silicon oxynitride or the like, and may be a barrier film or a buffer film according to the present invention. These ceramic films may be formed by vapor deposition, plasma CVD, or the like as described above, and the manufacturing method is not limited. The film thickness is in the range of 1 to 2000 nm, preferably 20 to 1000 nm.

  Hereinafter, specific examples of the sealed organic EL device of the present invention will be shown.

  FIG. 6 shows an example of an organic EL device sealed with the gas barrier resin substrate of the present invention. After forming each layer of an organic EL element composed of an anode, a light emitting layer, an organic layer, and a cathode on the gas barrier resin substrate of the present invention, the first ceramic layer according to the present invention, A gas barrier resin base material having a second ceramic layer and a third ceramic layer is stacked on the cathode, adhered, adhered around the element using an adhesive, and sealed, and an organic EL device example is shown in a cross-sectional configuration diagram Show. In the figure, an anode 6 made of ITO, an organic layer (a hole transport layer, a light emitting layer, an electron transport layer) on a gas barrier resin substrate B in which the first, second and third ceramic layers according to the present invention are sequentially formed. 7) and cathode 8 are sequentially laminated to form an organic EL element. Further, the gas barrier resin base material B of the present invention is bonded to the gas barrier layer by an adhesive C around the element. And sealed. The arrow indicates the direction of light extraction.

  FIG. 7 shows an example of another organic EL device sealed with the gas barrier resin substrate of the present invention. That is, after each of the organic EL element layers composed of an anode, a light emitting layer, an organic layer, and a cathode is similarly formed on the gas barrier resin substrate of the present invention, it is further formed into another sealing film S, in this case, a resin laminate. It is a cross-sectional block diagram which shows the example of the organic EL element which covered and sealed the metal foil (aluminum foil) by which (polymer film) was carried out.

  As the sealing film S, a ceramic layer S1 is formed on a metal (aluminum) foil S2, and the ceramic layer S1 side is bonded so as to be in contact with the cathode. The arrow indicates the light extraction direction.

  For sealing the organic EL element according to the present invention, an inorganic material such as glass having a low water vapor transmission rate and low gas transmission rate can be used in addition to the base material such as the sealing film.

  The example of the organic EL device which sealed the organic EL element using the glass-made sealing can in FIG. 8 was shown.

  In the figure, 101 is a gas barrier resin substrate of the present invention provided with a transparent electrode, on which an organic EL layer 102 comprising a hole injection / transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and the like. Then, a cathode 103 is formed to produce an organic EL element, and a sealing element produced by irradiating and bonding an ultraviolet lamp using a glass sealing can 104 and an ultraviolet curable adhesive 107 is shown. In addition, 105 is barium oxide of a water catching agent. The thickness of the glass sealing can is about 0.1 to 1.0 mm.

  In addition, as barium oxide which is a water trapping agent, for example, high-purity barium oxide powder manufactured by Aldrich is pasted using a fluororesin semi-permeable membrane (Microtex S-NTF8031Q manufactured by Nitto Denko) with an adhesive. It can be made by attaching. In addition, water replenishers commercially available from Japan Coretex Co., Ltd., Futaba Electronics Co., Ltd., and the like can also be preferably used.

  Even when these glass sealing cans and other sealing materials are used, these organic EL layers and cathodes are formed on the gas barrier resin base material without contacting them with the atmosphere. For example, in a nitrogen atmosphere (for example, a glove box substituted with high-purity nitrogen gas having a purity of 99.999% or more is used), it is preferable to have a sealed structure after the inside is replaced with nitrogen.

  Moreover, in forming the sealing structure, not only the sealing structure using the glass sealing can, but a water-absorbing substance is disposed in the sealing space, or a water-absorbing layer or the like is included in the structure. A layer that absorbs water vapor may be provided.

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

(1) Anode / light emitting layer / electron transport layer / cathode (2) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (4) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (5) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (anode)
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. As the anode, a thin film is formed by vapor deposition or sputtering of these electrode materials, or the aforementioned (atmospheric pressure) plasma CVD method. A pattern having a desired shape may be formed by photolithography, or a pattern may be formed through a mask at the time of formation. When light emission is extracted from the anode, the transmittance is set to be greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. Further, the film thickness 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.

  A gas barrier resin substrate with a transparent conductive film is formed by forming a transparent conductive film serving as an anode or a metal thin film serving as a cathode on the gas barrier resin substrate having the gas barrier thin film laminate according to the present invention on a resin substrate. If this is used, an organic EL element can be similarly formed by forming the following organic thin film layer and the other electrode. Any electrode material may be formed on the resin substrate, but it is preferable to produce a transparent conductive film to be an anode in terms of production or configuration.

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

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

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

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

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

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

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

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

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

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

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

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

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

  International Publication No. 00/70655 pamphlet, Japanese Patent Laid-Open No. 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859. Gazette, 2002-299060, 2001-313178, 2002-302671, 2001-345183, 2002-324679, WO 02/15645, JP-A-2002 No. 332291, No. 2002-50484, No. 2002-332292, No. 2002-83684, No. 2002-540572, No. 2002-117978, No. 2002-338588, 002-170684, 2002-352960, WO 01/93642, JP-A 2002-50483, 2002-100476, 2002-173684, 2002-35982 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>
The light-emitting host used in the present invention has a mass ratio of 20% or more among compounds contained in the light-emitting layer, and a phosphorescence quantum yield of phosphorescence emission is 0 at room temperature (25 ° C.). Less than .01.

  In the light emitting layer used in the present invention, a plurality of known host compounds may be used in combination as a host compound. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. As these known host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature) are preferable.

  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 in addition to the above are suitable. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The display 111 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

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

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

  The display portion A includes a wiring portion including a plurality of scanning lines 115 and data lines 116, a plurality of pixels 113, and the like on a substrate. The main members of the display unit A will be described below. FIG. 9 shows a case where the light emitted from the pixel 113 is extracted in the direction of the white arrow (downward).

  The scanning lines 115 and the plurality of data lines 116 in the wiring portion are each made of a conductive material, and the scanning lines 115 and the data lines 116 are orthogonal to each other in a grid pattern and are connected to the pixels 113 at the orthogonal positions (see FIG. Not shown).

  When a scanning signal is applied from the scanning line 115, the pixel 113 receives an image data signal from the data line 116, and emits light according to the received image data. Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.

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

  FIG. 11 is a schematic diagram of a pixel.

  The pixel includes an organic EL element 120, a switching transistor 121, a driving transistor 122, a capacitor 123, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 120 for a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 11, an image data signal is applied from the control unit B to the drain of the switching transistor 121 via the data line 116. When a scanning signal is applied from the control unit B to the gate of the switching transistor 121 via the scanning line 115, the switching transistor 121 is turned on, and the image data signal applied to the drain is supplied to the capacitor 123 and the driving transistor 122. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 123 is charged according to the potential of the image data signal, and the drive of the drive transistor 122 is turned on. The drive transistor 122 has a drain connected to the power line 117 and a source connected to the electrode of the organic EL element 120, and the power transistor 117 is connected to the organic EL element 120 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 115 by the sequential scanning of the control unit B, the driving of the switching transistor 121 is turned off. However, even if the driving of the switching transistor 121 is turned off, the capacitor 123 maintains the potential of the charged image data signal, so that the driving of the driving transistor 122 is kept on and the next scanning signal is applied. Until then, the organic EL element 120 continues to emit light. When the scanning signal is next applied by sequential scanning, the driving transistor 122 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 120 emits light.

  That is, the light emission of the organic EL element 120 is performed by providing the switching transistor 121 and the drive transistor 122 which are active elements for the organic EL element 120 of each of the plurality of pixels, and the light emission of the organic EL element 120 of each of the plurality of pixels 113. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 120 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.

  The potential of the capacitor 123 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

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

  FIG. 12 is a schematic diagram of a passive matrix display device. In FIG. 12, a plurality of scanning lines 115 and a plurality of image data lines 116 are provided in a lattice shape so as to face each other with the pixel 113 interposed therebetween.

  When the scanning signal of the scanning line 115 is applied by sequential scanning, the pixel 113 connected to the applied scanning line 115 emits light according to the image data signal. In the passive matrix method, there is no active element in the pixel 113, and the manufacturing cost can be reduced.

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

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

  As a layer structure of the organic EL element for obtaining a plurality of emission colors, a method of having a plurality of emission dopants in one emission layer, a plurality of emission layers, and an emission wavelength of each emission layer. Examples thereof include a method in which different dopants are present and a non-light emitting intermediate layer is appropriately disposed between the respective light emitting layers, and a method in which minute pixels emitting light having different wavelengths are formed in a matrix.

  In the white organic EL device according to the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. When patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire element layer may be patterned.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the platinum complex which concerns on this invention so that it may correspond to the wavelength range corresponding to CF (color filter) characteristic, and well-known Any one of the light emitting materials may be selected and combined to be whitened.

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

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

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

Example 1
[Preparation of Sample 1]
A transparent resin substrate (polyethylene terephthalate (PET) film with a clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd., PET thickness 125 μm, CHC thickness 6 μm) by the atmospheric pressure plasma method using the apparatus shown in FIG. ), A first ceramic layer (100 nm) and a second ceramic layer (50 nm) were sequentially formed under the following thin film formation conditions to obtain Sample 1.

(Formation of the first ceramic layer)
<First ceramic layer mixed gas composition>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.5% by volume
Additive gas: Oxygen gas 5.0% by volume
<Filming conditions for the first ceramic layer>
1st electrode side Power supply type
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 90 ° C
(Formation of second ceramic layer)
<Second ceramic layer mixed gas composition>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Tetraethoxysilane 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
<Second ceramic layer deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10W / cm ²
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 90 ° C
[Preparation of Samples 2 to 5]
In the preparation of Sample 1, the concentration of the raw material (tetraethoxysilane) in the thin film forming gas during film formation, the first electrode side power source (low frequency power source, 80 kHz), and the second electrode side power source (high frequency power source, 13.56 MHz) Samples 2 to 5 were prepared in the same manner except that each output power source was changed as shown in Table 1.

[Preparation of Sample 6]
Transparent resin base material (polyethylene terephthalate (PET) film with clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd., PET thickness 125 μm, CHC thickness 6 μm)) using a plasma CVD apparatus Model PD-270STP manufactured by Samco On top, a first ceramic layer (100 nm) and a second ceramic layer (50 nm) were sequentially formed under the following thin film formation conditions to obtain Sample 6.

(Formation of the first ceramic layer)
Oxygen pressure: 53.2Pa
Reaction gas: Tetraethoxysilane (TEOS) 5 sccm (standard cubic centimeter per minute) concentration 0.5%
Power: 100W at 13.56MHz
Substrate holding temperature: 120 ° C
The composition of the first ceramic layer was SiO ₂ and the density was 2.13.

(Formation of second ceramic layer)
In the film formation conditions of the first ceramic layer, the application of electric power was reversed, the substrate holding side was grounded, and high frequency power was applied to the counter electrode side to perform film formation. The composition of the second ceramic layer was SiO _1.48 C _0.96 and the density was 2.02.

  Table 1 shows the formation conditions of each sample. In addition, “-” described in the section of gas pressure in Table 1 represents atmospheric pressure.

<Measurement of characteristic values of each sample>
(Measurement of film density)
It measured by the X-ray reflectivity measuring method.

  As the measuring apparatus, MXP21 manufactured by Mac Science Co., Ltd. was used, copper was used as the target of the X-ray source, and it was operated at 42 kV and 500 mA. A multilayer parabolic mirror was used for the incident monochromator. The entrance slit is 0.05 mm x 5 mm, the light receiving slit is 0.03 mm x 20 mm, and the 2θ / θ scan method is used to measure from 0 to 5 ° by the FT method with a step width of 0.005 ° and a step of 10 seconds. It was. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting was performed using No. 1, each parameter was determined so that the residual sum of squares of the actual measurement value and the footing curve was minimized, and the thickness and density of the laminated film were determined from each parameter.

[Measurement of carbon content]
The carbon content of the produced first, second, and third ceramic layers was measured by XPS (atomic concentration%). The carbon content is an atomic number concentration% calculated by the following XPS method and is defined below.

Atomic concentration (at%) = 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.

(Measurement of elastic modulus)
Using a nano indenter (Nano Indenter TMXP / DCM) manufactured by MTS System, measurement was performed with a triangular pyramid (Berkovic type) composed of a diamond chip.

(Measurement of compressive stress)
Each ceramic layer was formed to a thickness of 1 μm on a quartz glass having a thickness of 100 μm, a width of 10 mm, and a length of 50 mm, and the compressive stress (residual stress, MPa) was measured with a thin film property evaluation apparatus MH4000 manufactured by NEC Saneisha. .

  Table 2 shows the characteristic values obtained as described above.

<< Evaluation of gas barrier resin base material >>
[Evaluation 1: Evaluation of gas barrier properties]
About each produced said gas-barrier resin base material, according to the following method, the water-vapor-permeation rate was measured and this was made into the scale of gas-barrier property.

(Measurement of water vapor transmission rate)
The water vapor transmission rate was measured with a water vapor transmission rate measuring device PERMATRAN-W 3/33 MG module manufactured by MOCON in accordance with a method (40 ° C., 90% RH) defined in JIS K 7129B.

[Evaluation 2: Evaluation of adhesion (forced peel test)]
Each gas barrier resin base material produced above was cut into a 20 mm wide strip, and two pieces were cured by UV and heat using an epoxy adhesive (Three Bond 3124C) as shown in FIG. Area 20 × 20 mm). Immediately after bonding, and after storage at 60 ° C. and 90% RH for 500 hours, the film was pulled in both directions with a constant load. As a result, the case where the peeled area of the ceramic film was less than 5% was judged as ◯, and the case where the ceramic film was peeled off at an area of 5% or more was judged as x.

[Evaluation 3: Evaluation of bending resistance]
Under an environment of 25 ° C. and 55% RH, each gas barrier resin base material was wound around a 100 mmφ stainless steel cylinder with the ceramic layer forming surface facing inside, and then spread. After repeating this operation 20 times, the gas barrier layer surface of each gas barrier resin substrate was observed with a microscope and the water vapor transmission rate was measured according to the following formula, and the bending resistance was evaluated according to the following criteria.

Deterioration rate of water vapor transmission rate (%) = 100−water vapor transmission rate after winding operation / water vapor transmission rate before winding × 100
○: No cracks are generated in the ceramic layer, and the deterioration rate of the water vapor transmission rate is less than 5% before and after the winding operation. Δ: The generation of extremely small cracks is observed in the ceramic layer, and before and after the winding operation. Deterioration rate of water vapor transmission rate of 5% or more and less than 10% x: Clear cracks are observed in the ceramic layer, and the deterioration rate of water vapor transmission rate before and after the winding operation is 10% or more Table 3 shows the evaluation results obtained by the above.

  As is apparent from the results shown in Table 3, the gas barrier resin base material of the present invention having a ceramic layer having the film characteristics defined in the present invention has an excellent gas barrier property (water vapor barrier property) relative to the comparative example. In addition, it can be seen that the film has good adhesion even immediately after film formation and after storage under high temperature and high humidity conditions, and the formed gas barrier layer is excellent in bending resistance.

Example 2
[Preparation of Sample 7]
After forming a smoothing layer on both surfaces of a resin base material (polyester naphthalate manufactured by Teijin DuPont Films, Inc., thickness 125 μm) under the following conditions, the first ceramic layer ( 100 nm) and the second ceramic layer (50 nm) were sequentially formed into thin films to obtain Sample 7.

(Formation of smoothing layer)
The following smoothing layer composition was applied on one side of the resin base material so that the dry film thickness was 6.5 μm, and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured. Furthermore, the smoothing layer was provided in the same procedure on the other side, and the resin base material which has a smoothing layer on both surfaces was produced.

<Smoothing layer composition>
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer or higher component 20 parts by mass Diethoxybenzophenone (UV photoinitiator) 2 parts by mass Methyl ethyl ketone 50 Part by mass Ethyl acetate 50 parts by mass Isopropyl alcohol 50 parts by mass The above composition was dissolved with stirring.

[Production of Samples 8 to 12]
Samples 8 to 12 were produced in the same manner as in the production of Sample 7 except that the production conditions of the ceramic layers were changed in the same manner as in Samples 2 to 6, respectively.

<< Evaluation of characteristics of each sample >>
The gas barrier resin base materials of Samples 7 to 12 were each used as an organic EL display substrate, on which a transparent electrode constituting an anode electrode, a hole transport layer having a hole transport property, a light emitting layer, a hole blocking layer, An electron transport layer, an electron injection layer, and a back electrode serving as a cathode were laminated.

Transparent electrode: ITO 150nm
Hole transport layer: m-MTDATXA 40 nm
Light emitting layer:
Light emitting layer A: CDBP, Ir-15 (3%) 25 nm
Intermediate layer 1: L-98 3 nm
Light emitting layer B: CDBP, Ir-16 (8%) 10 nm
Hole blocking layer: L-98 10 nm
Electron transport layer: Alq ₃ 35 nm
Cathode buffer layer: lithium fluoride 0.5 nm
Cathode: Aluminum 110nm

  Furthermore, the same gas barrier resin base material as that used as the substrate is stacked on each of these layers via a UV (thermal) curable epoxy-based sealing adhesive material (ThreeBond 3124C), and the organic layers are adhered, adhered, and sealed. EL elements (OLED) 7 to 12 were prepared, and 50 times magnified photographs were taken after storage at 60 ° C., 90% RH, and 500 hours, respectively. As a result, in the organic EL device produced using the gas barrier resin substrate of the present invention, the generation of the non-light emitting region at the edge portion was not recognized, but the organic EL device produced using the gas barrier resin substrate of the comparative example. In the EL element, the presence of a non-light emitting region was observed at a part of the edge. This is presumably because the comparative example has poor adhesiveness, so that deterioration is caused by partial barrier property deterioration due to film peeling at the part where the gas barrier resin base materials are bonded together. As described above, it was confirmed that the gas barrier resin substrate of the present invention maintained the performance excellent in the water vapor blocking effect and the oxygen blocking effect with respect to the comparative example.

It is sectional drawing which shows the layer structural example of the gas barrier resin base material of this invention. It is the schematic which showed an example of the jet-type atmospheric pressure plasma discharge processing apparatus. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the system which processes a base material between counter electrodes. 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. It is a section lineblock diagram showing an example of an organic EL device sealed using a gas barrier resin substrate of the present invention. An example of another organic EL device sealed with the gas barrier resin substrate of the present invention is shown. It is a figure which shows the example of the organic EL device which sealed the organic EL element using the glass sealing can. It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. The schematic diagram of the display part A is shown. A schematic diagram of a pixel is shown. The schematic diagram of the display apparatus by a passive matrix system is shown. It is a figure which shows the embodiment of a forced peeling test.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin base material 2 Polymer film 3 1st ceramic layer 4 2nd ceramic layer 5 3rd ceramic layer B Gas barrier resin base material C Adhesive 10 Plasma discharge processing apparatus 11 1st electrode 12 2nd electrode 21 1st Power source 30 Plasma discharge treatment device 32 Discharge space 35 Roll rotating electrode 35a Roll electrode 35A Metal base material 35B Dielectric 36 Square tube type fixed electrode group 40 Electric field applying means 41 First power supply 42 Second power supply 50 Gas supplying means 51 Gas generation Device 52 Air supply port 53 Air exhaust port 60 Electrode temperature adjusting means G Thin film forming gas G ° Gas in plasma G ′ Treatment exhaust gas 101 Gas barrier resin substrate with anode 102 Organic EL layer 103 Cathode 104 Glass sealing can 105 Barium oxide 107 Adhesive 111 Display 113 Pixel 115 Scan Line 116 Data Line 117 Power line 120 Organic EL element 121 Switching transistor 122 Drive transistor 123 Capacitor

Claims (11)

In a gas barrier resin substrate having a gas barrier layer in which a ceramic layer containing at least two layers of silicon oxide is laminated on at least one surface of a transparent resin substrate, at least one of the ceramic layers has an elastic modulus of 5 GPa or more, A gas barrier resin base material, wherein the gas barrier resin base material is a first ceramic layer containing silicon oxide of 20 GPa or less, and the compression stress of the gas barrier layer is 0 MPa or more and 20 MPa or less. The first ceramic layer has a laminated structure in which a second ceramic layer containing silicon oxide is formed on the first ceramic layer, and the second ceramic layer has an elastic modulus E1 with respect to the elastic modulus E1. 2. The gas barrier resin substrate according to claim 1, wherein a ratio (E2 / E1) of an elastic modulus E2 of the ceramic layer is 1.0 or more and 10.0 or less. The gas barrier resin substrate according to claim 1 or 2, wherein the carbon content of the first ceramic layer is 0.2% or more and 4.9% or less in terms of atomic number concentration. 4. The gas barrier resin substrate according to claim 1, wherein the film density of the first ceramic layer is 1.80 or more and 2.15 or less. The gas barrier resin base material according to any one of claims 1 to 4, wherein the first ceramic layer is formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied. 6. The gas barrier resin substrate according to claim 1, wherein the carbon content of the second ceramic layer is 0.1% or less in terms of atomic number concentration. 7. The gas barrier resin substrate according to claim 1, wherein a film density of the second ceramic layer is 2.15 or more and 2.50 or less. The gas barrier resin substrate according to any one of claims 1 to 7, wherein the second ceramic layer is formed by an atmospheric pressure plasma method in which two or more electric fields having different frequencies are applied. The gas barrier resin according to any one of claims 1 to 8, wherein the water vapor permeability is 1 x 10 ^-7 g / m ² / day or more and less than 0.01 g / m ² / day. Base material. An electrode and an organic compound layer are formed at least on the gas barrier resin substrate according to any one of claims 1 to 9, and a sealing member is disposed so as to cover the electrode and the organic compound layer. The organic electroluminescence device, wherein the sealing member and the gas barrier resin base material are bonded and sealed. The organic electroluminescent device according to claim 10, wherein the sealing member is the gas barrier resin base material according to claim 1.

Images