JPWO2014208449A1 - Organic electroluminescence device and method for manufacturing the same - Google Patents

Abstract

The subject of this invention is providing the organic electroluminescent element which has flexibility and the outstanding contrast ratio, and is excellent in heat-resistant storage stability. The organic electroluminescence device of the present invention is an organic electroluminescence device comprising at least a first electrode, an organic light emitting layer, and a second electrode in this order on a resin substrate, wherein the first electrode and the second electrode are Each is a transparent electrode, and has a polysilazane modified layer between the first electrode and the resin substrate, and a light absorbing layer containing a black material on the opposite side of the organic light emitting layer of the second electrode. It is characterized by having.

Description

  The present invention relates to an organic electroluminescence element and a method for manufacturing the same. More specifically, the present invention relates to an organic electroluminescence element having flexibility and an excellent contrast ratio and excellent in heat-resistant storage stability and a method for producing the same.

  At present, a light-emitting element using electroluminescence (EL) of an organic material is attracting attention as a thin light-emitting material.

  A so-called organic electroluminescence element (hereinafter also referred to as an organic EL element) is a thin-film type complete solid-state element that can emit light at a low voltage of about several V to several tens V, and has high luminance, high luminous efficiency, thin thickness, It has many excellent features such as light weight. For this reason, it attracts attention as a surface light emitter such as backlights of various displays, display boards such as signboards and emergency lights, and illumination light sources. In particular, in recent years, flexible organic electroluminescence elements using a resin base material having a thin and lightweight gas barrier film have attracted attention.

  On the other hand, there is a demand for good appearance with an excellent contrast ratio. For example, in Patent Document 1, black aluminum-tungsten or aluminum is used in order to eliminate unnatural metallic luster due to a metal electrode layer when no light is emitted. A technique for obtaining a high contrast ratio by inserting a molybdenum alloy between an organic light emitting layer and a metal electrode layer is disclosed. However, the influence of reflection by the metal electrode layer cannot be completely eliminated, and it has been found that there is room for improvement in order to obtain an excellent contrast ratio.

  Patent Document 2 discloses a technique for achieving an excellent contrast ratio by disposing a black material so as to be in contact with an electrode on one side of an organic electroluminescence element that emits light on both sides. However, as a result of confirmation by the present inventor, it has been found that thermal degradation of the member becomes a problem due to the effect of the black material storing heat when used outdoors. Especially when using a resin base material, it is found that the thermal conductivity difference between the resin base material and the electrode is large, so that heat is stored between the resin base material and the electrode, and deterioration of the electrode becomes a problem. did.

Japanese Patent No. 3165413 Japanese Patent No. 3711683

  The present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is to provide an organic electroluminescence element having flexibility and an excellent contrast ratio and excellent in heat-resistant storage stability and a method for producing the same. That is.

  In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, etc., an organic electroluminescence comprising at least a first electrode, an organic light emitting layer, and a second electrode in this order on a resin substrate. An element, wherein the first electrode and the second electrode are both transparent electrodes, have a polysilazane modified layer between the first electrode and the resin substrate, and the organic light emitting layer of the second electrode It was found that an organic electroluminescence device having a light absorption layer on the opposite side of the surface can provide an organic electroluminescence device having flexibility and excellent contrast ratio and excellent heat-resistant storage stability. It was.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. An organic electroluminescence device comprising at least a first electrode, an organic light emitting layer, and a second electrode in this order on a resin base material, both of the first electrode and the second electrode being transparent electrodes, A polysilazane modified layer is provided between one electrode and the resin base material, and a light absorption layer containing a black material is provided on the opposite side of the organic light emitting layer of the second electrode. Organic electroluminescence device.

  2. 2. The organic electroluminescence device according to item 1, wherein the polysilazane modified layer contains at least one compound selected from polysilazane and a polysilazane modified product.

  3. At least one of the first electrode and the second electrode is an electrode layer having a thickness of 30 nm or less formed using silver or an alloy containing silver as a main component. The organic electroluminescent element of the item.

  4). The method for producing an organic electroluminescence device according to any one of items 1 to 3, wherein the polysilazane modified layer is modified by irradiating the polysilazane-containing layer with vacuum ultraviolet light. A method for producing an organic electroluminescence element, comprising:

  By the above means of the present invention, it is possible to provide an organic electroluminescence device having flexibility and excellent contrast ratio and excellent in heat resistant storage stability and a method for producing the same.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  The organic electroluminescence device of the present invention has a polysilazane modified layer formed between the resin substrate according to the present invention and the first electrode, and contains a black material on the opposite side of the organic light emitting layer of the second electrode. It is characterized by having a light absorbing layer.

  The light absorption layer containing a black material is used to reduce light reflection inside the metal electrode and the element and increase the contrast ratio. In particular, when the first electrode and the second electrode are transparent electrodes, the contrast ratio can be greatly improved because the reflected light inside the element that passes through the electrodes can be absorbed by the black material of the light absorption layer.

  However, when the organic electroluminescence element is used outdoors, the thermal deterioration of the member becomes a problem due to the influence of external heat stored inside the element by the black material. In particular, when a resin base material is used, since the difference in thermal conductivity between the resin base material and the electrode is large, heat is stored in the part, and thermal deterioration of the electrode becomes a problem.

  This is presumed to be caused by the fact that the difference in the thermal conductivity coefficient between the resin base material and the electrode material is too large, resulting in heat storage at the material interface. Therefore, by providing a heat conduction relaxation layer that fills the gap of the heat conduction coefficient between the resin base material and the electrode, it is considered that heat conduction is facilitated and the influence of the heat storage can be reduced.

An SiO ₂ film can be considered as such a material (for example, the thermal conductivity coefficient is measured by a flash method in terms of resin: 0.1 to 0.2 W / mK, SiO ₂ : 0.75 W / mK, ITO: 3. 05 W / mK, and Ag: 420 W / mK.)

However, for example, the SiO ₂ film formed by the sputtering method has a non-smooth surface, so that the heat radiation distribution is uneven and the heat conduction effect is not so high as expected. Further, in the formation of the SiO ₂ film by the sol-gel method, the surface is smooth, but since a high heat treatment is required at the time of formation, it is difficult to form on the resin base material, and application of these methods is difficult.

The present inventor has found that the polysilazane modified layer is used as a heat conductive material having a high surface smoothness and uniform heat dissipation and can be applied to formation on a resin substrate. The polysilazane modified layer has a high surface smoothness, and therefore has a uniform heat dissipation property, and does not require a high heat treatment to be formed at the same time. Therefore, it can be formed on a resin base material. It is presumed that the material can be used as a material to overcome the above-mentioned drawbacks of SiO ₂ film formation.

The figure which shows schematic structure of the organic EL element of this invention Diagram showing silicon distribution curve, oxygen distribution curve and carbon distribution curve The figure which expanded the carbon distribution curve shown in FIG. Diagram showing the refractive index profile of the gas barrier layer The figure which shows the structure of the manufacturing apparatus of a gas barrier layer

  The organic electroluminescence device of the present invention is an organic electroluminescence device comprising at least a first electrode, an organic light emitting layer, and a second electrode in this order on a resin substrate, wherein the first electrode and the second electrode are Both are transparent electrodes, have a polysilazane modified layer between the first electrode and the resin base material, and a light absorbing layer containing a black material on the opposite side of the organic light emitting layer of the second electrode. It is characterized by having. This feature is a technical feature common to the inventions according to claims 1 to 4.

  As an embodiment of the present invention, from the viewpoint of manifestation of the effect of the present invention, the polysilazane modified layer contains at least one compound selected from polysilazane and a polysilazane modified product. Is more preferable, and heat conductivity can be improved.

  Furthermore, at least one of the first electrode and the second electrode is an electrode layer having a thickness of 30 nm or less formed using silver or an alloy containing silver as a main component. Flexibility can be satisfied, which is preferable.

  In addition, adopting the polysilazane-modified layer in a manufacturing method in which the polysilazane-containing layer is modified by irradiating with vacuum ultraviolet light improves the smoothness of the surface of the polysilazane-modified layer and improves heat conduction. This is a preferred production method because the properties can be further improved.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<Outline of the organic electroluminescence device of the present invention>
The organic electroluminescence device of the present invention is an organic electroluminescence device comprising at least a first electrode, an organic light emitting layer, and a second electrode in this order on a resin substrate, wherein the first electrode and the second electrode are Both are transparent electrodes, have a polysilazane modified layer between the first electrode and the resin base material, and a light absorbing layer containing a black material on the opposite side of the organic light emitting layer of the second electrode. It is characterized by having.

<Details of the organic electroluminescence device of the present invention>
[Configuration of organic EL element]
An example of the configuration of the organic EL device of the present invention is shown in FIG. However, the present invention is not limited to this.

  The organic EL element 50 shown in FIG. 1 includes a resin base material 26, a gas barrier layer 27, a polysilazane modified layer 11, an organic light emitting layer 45, and a second electrode 46 serving as a cathode on a first electrode 25 serving as an anode. The structure is laminated and further solid-sealed by a resin layer 47 containing an adhesive and a sealing member 48. The light absorbing layer containing the black material according to the present invention is provided on the side opposite to the organic light emitting layer of the second electrode 46, and even if a layer containing a black material is formed as the light absorbing layer. Alternatively, the resin layer 47 may contain a black material, a light absorbing layer containing the black material may be formed or bonded to the surface of the sealing member 48, and further, the sealing The stop member 48 itself may contain a black material.

  Since the first electrode 25 used as the anode is a transparent electrode, therefore, the organic EL element 50 causes the generated light (hereinafter referred to as emission light h) to be at least on the resin base material 26 side (see FIG. 26a) is configured as a bottom emission type.

  Further, the overall layer structure of the organic EL element 50 is not limited to the above, and may be a general layer structure. Here, the first electrode 25 is disposed on the anode (ie, anode) side, and the conductive layer 12 mainly functions as the anode, while the second electrode 46 functions as the cathode (ie, cathode).

  In this case, for example, the organic light emitting layer 45 has [hole injection layer 45a / hole transport layer 45b / light emission layer 45c / electron transport layer 45d / electron injection layer 45e] in this order on the first electrode 25 which is an anode. Although the laminated structure can be illustrated, it is necessary to have the light emitting layer 45c comprised using the base material at least among these. The hole injection layer 45a and the hole transport layer 45b may be provided as a hole transport / injection layer having a hole transport property and a hole injection property. The electron transport layer 45d and the electron injection layer 45e may be provided as a single layer having electron transport properties and electron injection properties. Of these organic light emitting layers 45, for example, the electron injection layer 45e may be made of a non-base material.

  Another configuration of the organic EL element of the present invention is an example in which the first electrode functions as a cathode and the second electrode functions as an anode. In this case, the configuration of [hole injection layer 45a / hole transport layer 45b / light emitting layer 45c / electron transport layer 45d / electron injection layer 45e] can be exemplified from the second electrode side.

  In addition to these layers, the organic light-emitting layer 45 may be laminated with a hole blocking layer, an electron blocking layer, or the like as necessary. Furthermore, the light emitting layer 45c has each color light emitting layer for generating emitted light in each wavelength region, and each of these color light emitting layers is laminated via a non-light emitting intermediate layer to form a light emitting layer unit. Also good. The intermediate layer may function as a hole blocking layer and an electron blocking layer. Further, the second electrode 46 serving as a cathode may also have a laminated structure as required. In such a configuration, only a portion where the organic light emitting layer 45 is sandwiched between the first electrode 25 and the second electrode 46 becomes a light emitting region in the organic EL element 50.

  In addition, the organic EL element 50 is solidified by attaching a sealing member 48 on one surface of the first electrode 25 via a resin layer 47 covering the organic light emitting layer 45 and the second electrode 46. It is sealed. Solid sealing of the organic EL element 50 is performed by applying uncured resin material to a bonding surface of the sealing member 48 or the resin base material 26 and the second electrode 46 of the first electrode 25 at a plurality of locations. The resin base material 26 and the sealing member 48 are pressed and integrated with each other in a heated state with the resin material interposed therebetween.

  The end portion of the first electrode 25 has a shape of an extraction electrode, and the first electrode 25 and an external power source (not shown) are electrically connected via the extraction electrode.

  In the organic EL device 50 of the present invention, the resin base material, the gas barrier layer, the polysilazane modified layer, the first electrode serving as the anode, the organic light emitting layer, the second electrode serving as the cathode, and the sealing member are all flexible. It is preferable to have properties.

  The term “flexibility” as used herein means that the material constituting the organic EL element and the organic EL element itself are wound around a φ (diameter) 50 mm roll and are not cracked before and after winding with a constant tension. That means.

  Hereinafter, each component of the organic EL element of this invention is demonstrated sequentially.

(1) Light Absorbing Layer The organic EL device of the present invention includes a light absorbing layer containing the black material according to the present invention, so that the light absorbing layer absorbs scattered light and reflected light inside the device. , Has a function of increasing the contrast ratio. The light absorption rate of the light absorption layer preferably absorbs 95% or more of incident light in the light wavelength range of 380 to 700 nm, more preferably 99% or more, and further preferably 99.9% or more. The light absorptance can be measured with a commercially available spectrophotometer. For example, it can be measured by mounting an integrating sphere on a Hitachi spectrophotometer U-4100 manufactured by Hitachi or a UV-3101 spectrophotometer manufactured by Shimadzu Corporation.

  The black material according to the present invention is not particularly limited, and a black material such as carbon black, a silver paste material containing carbon particles, aluminum-tungsten, and aluminum-molybdenum, or a commercially available ND filter may be used. it can.

  As described above, the light absorption layer containing the black material according to the present invention is provided on the side opposite to the organic light emitting layer of the second electrode, and the second electrode is a transparent electrode. It has a function of absorbing the scattered light and reflected light transmitted through the light.

  In order to provide the light absorbing layer containing the black material, a layer containing the black material may be formed on the surface of the second electrode 46 opposite to the organic light emitting layer 45, or the second electrode 46 may be sealed. A layer containing a black material may be formed between the stop members 48, a black material may be contained in the resin layer 47, and a film is formed or bonded to the surface of the sealing member 48. Further, the sealing member 48 itself may contain a black material.

  For example, by applying a photoresist material containing carbon black on the surface of the second electrode 46 opposite to the organic light emitting layer by a spin coating method and baking it, the light absorption of the thin film containing carbon black is achieved. A layer may be formed.

  Further, a commercially available ND filter (for example, ND = 4.0) manufactured by Fuji Film Co., Ltd. may be inserted between the second electrode and the sealing member, or the sealing member itself An ND filter may be used.

  (2) Polysilazane modified layer The polysilazane modified layer according to the present invention functions as a heat conduction relaxation layer, and contains at least one compound of polysilazane and a polysilazane modified product.

  The polysilazane modified layer is preferably a layer formed by subjecting a coating film of a polysilazane-containing liquid to a modification treatment by a modification means. This modified layer is mainly formed from a silicon oxide or a silicon oxynitride compound.

  As a method for forming a polysilazane modified layer, a layer containing a silicon oxide or a silicon oxynitride compound is formed by applying a coating solution containing at least one polysilazane compound on a substrate and then performing a modification treatment. The method of forming is mentioned.

  Silicon oxide or silicon oxynitride compound for forming a polysilazane modified layer of silicon oxide or silicon oxynitride compound is supplied as a gas as in CVD (Chemical Vapor Deposition). Rather than being supplied, a more uniform and smooth layer can be formed by applying to the substrate surface. In the case of the CVD method or the like, it is known that foreign substances called unnecessary particles are generated in the gas phase simultaneously with the step of depositing the source material having increased reactivity in the gas phase on the surface of the substrate. As these generated particles accumulate, the smoothness of the surface decreases. In the coating method, it is possible to suppress the generation of these particles by preventing the raw material from being present in the gas phase reaction space. For this reason, a smooth surface can be formed by using a coating method.

(Coating film of polysilazane-containing liquid)
The coating film of the polysilazane-containing liquid is formed by applying a coating liquid containing a polysilazane compound in at least one layer on the substrate.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

“Polysilazane” is a polymer having a silicon-nitrogen bond, and is a ceramic precursor inorganic polymer such as SiO ₂ , Si ₃ N ₄ composed of Si—N, Si—H, N—H, etc., and both intermediate solid solutions SiOxNy. is there. Polysilazane is represented by the following general formula (A).

Formula (A)
-[Si (R ₁ ) (R ₂ ) -N (R ₃ )]-
In order to apply the film base material without damaging the film base material, it is preferable that the film base material is converted to silica at a relatively low temperature as described in JP-A-8-112879.

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

Perhydropolysilazane, in which all of R ₁ , R ₂ , and R ₃ are hydrogen atoms, is particularly preferred from the viewpoint of the denseness as the obtained gas barrier film.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane is hard and brittle. The ceramic film can be provided with toughness, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

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

  As another example of polysilazane which is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the polysilazane represented by the above general formula (I) (Japanese Patent Laid-Open No. 5-238827), glycidol is reacted. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal obtained by adding metal fine particles Polysilazane containing fine particles JP-A-7-196986 publication), and the like.

  Specific examples of the organic solvent for preparing a liquid containing polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and fats. Ethers such as cyclic ethers can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed. Note that alcohol-based or water-containing solvents are not preferable because they easily react with polysilazane.

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

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

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

(Polysilazane-containing layer forming step)
The coating film of the polysilazane-containing liquid preferably has moisture removed before or during the modification treatment. Therefore, it is preferable to divide into the 1st process for the purpose of removing the solvent in a polysilazane content layer, and the 2nd process for the purpose of removing the water | moisture content in a polysilazane content layer after that.

  In the first step, drying conditions for mainly removing the solvent can be appropriately determined by a method such as heat treatment, but the conditions may be such that moisture is removed at this time. The heat treatment temperature is preferably high from the viewpoint of rapid treatment, but the temperature and treatment time are determined in consideration of thermal damage to the resin substrate. For example, when a PET substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the heat treatment temperature can be set to 200 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the substrate is reduced. If the heat treatment temperature is 200 ° C. or less, the treatment time can be set within 30 minutes.

  The second step is a step for removing moisture in the polysilazane-containing layer, and the method for removing moisture is preferably in a form maintained in a low humidity environment. Since the humidity in the low humidity environment varies depending on the temperature, a preferable form of the relationship between temperature and humidity is shown by the dew point temperature. A preferable dew point temperature is 4 degrees or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 degrees (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is (temperature 25 ° C./humidity 1%). ) −31 ° C. or lower, and the maintained time varies depending on the thickness of the polysilazane-containing layer. Under the condition that the thickness of the polysilazane-containing layer is 1 μm or less, the preferable dew point temperature is −8 ° C. or less, and the maintained time is 5 minutes or more. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

  As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes in the first step, the dew point of the second step is 4 degrees or less. The treatment time can be selected from 5 minutes to 120 minutes under conditions for removing moisture. The first process and the second process can be distinguished by changing the dew point, and can be classified by changing the dew point of the process environment by 10 degrees or more.

  The polysilazane-containing layer is preferably subjected to a modification treatment while maintaining its state even after moisture is removed in the second step.

(Water content of polysilazane-containing layer)
The water content of the polysilazane-containing layer can be detected by the following analysis method.

Headspace-gas chromatograph / mass spectrometry apparatus: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min), then heated to 150 ° C. at a rate of 10 ° C./min Column: DB-624 (0.25 mm × 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C, 30min
The water content in the polysilazane-containing layer is defined as a value obtained by dividing the water content obtained by the above analysis method by the volume of the polysilazane-containing layer, and preferably 0.1% in a state where moisture is removed by the second step. It is as follows. A more preferable moisture content is 0.01% or less (below the detection limit).

  This is a preferred mode for promoting the dehydration reaction of polysilazane converted to silanol by removing water before or during the modification treatment.

<Reforming treatment>
For the modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Production of a silicon oxide film or silicon oxynitride film by a substitution reaction of a silazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate such as plastic. For adaptation to plastic substrates, a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a lower temperature is preferable.
(Plasma treatment)
A known method can be used for the plasma treatment as the modification treatment, but atmospheric pressure plasma treatment is preferable. In the case of atmospheric pressure plasma treatment, nitrogen gas and / or Group 18 atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As an example of plasma processing, atmospheric pressure plasma processing will be described. Specifically, as described in International Publication No. 2007-026545, the atmospheric pressure plasma is one in which two or more electric fields having different frequencies are formed in the discharge space, and the first high-frequency electric field and the second high-frequency electric field are formed. It is preferable to form an electric field superimposed with the electric field.

In the atmospheric pressure plasma treatment, 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, The relationship with the intensity IV of the discharge start electric field is
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By adopting such discharge conditions, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and perform high-performance thin film formation. Can do.

  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 into a plasma state.

  Here, as the frequency of the first power supply, 200 kHz or less can be preferably used. 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, as the frequency of the second power source, 800 kHz or more can be preferably used. 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 formation of a high-frequency electric field from such two power sources is necessary for initiating discharge of a discharge gas having a high discharge start electric field strength by the first high-frequency electric field, and the second high-frequency electric field is high. A dense and good quality thin film can be formed by increasing the plasma density by the frequency and the high power density.

(UV irradiation treatment)
As a modification treatment method, treatment by ultraviolet irradiation is also preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and it is possible to produce silicon oxide films or silicon oxynitride films that have high density and insulation at low temperatures. It is.

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The conversion to ceramics is promoted, and the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the method according to the present embodiment, any commonly used ultraviolet ray generator can be used.

  In this example, “ultraviolet rays” generally refers to electromagnetic waves having a wavelength of 10 to 400 nm, but in the case of ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, preferably 210 to 210. An ultraviolet ray of 350 nm is used.

  In the irradiation with ultraviolet rays, the irradiation intensity and the irradiation time are set within a range where the substrate carrying the irradiated coating film is not damaged.

Taking the case of using a plastic film as a base material, for example, a lamp of 2 kW (80 W / cm × 25 cm) is used, and the strength of the base material surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ^2. The distance between the base material and the lamp is set so that the irradiation becomes 0.1 seconds to 10 minutes.

  Generally, when the substrate temperature during the ultraviolet irradiation treatment is 150 ° C. or higher, the substrate is damaged in the case of a plastic film or the like, such as deformation of the substrate or deterioration of strength. However, in the case of a highly heat-resistant film such as polyimide or a substrate such as metal, processing at a higher temperature is possible. Therefore, there is no general upper limit to the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generation methods include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. )), UV light laser, and the like. Also, when irradiating the polysilazane coating film with the generated UV light, the UV light from the source is reflected on the reflector and then applied to the coating film in order to achieve uniform irradiation to improve efficiency. Is desirable.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a substrate (eg, silicon wafer) having a polysilazane coating film on the surface can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet light source. The ultraviolet baking furnace itself is generally known, and for example, it is possible to use those manufactured by I-Graphics Co., Ltd. In addition, when the substrate having a polysilazane coating film on the surface is a long film, the ceramic is obtained by continuously irradiating ultraviolet rays in a drying zone having the ultraviolet ray generation source as described above while being conveyed. Can be The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate to be applied and the coating composition.

(Vacuum ultraviolet irradiation treatment; excimer irradiation treatment)
In the present embodiment, a particularly preferable method for the modification treatment is treatment by vacuum ultraviolet irradiation. The treatment with vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the silazane compound, and bonds of atoms are only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of.

As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used. 1. Excimer light emission is called an inert gas because atoms of rare gases such as Xe, Kr, Ar, and Ne do not form a molecule by chemically bonding. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ^{2 *} + Xe
Then, when the excited excimer molecule Xe ^{2 *} transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.

  Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. Is a very thin discharge called micro discharge. When the microdischarge streamer reaches the tube wall (dielectric), the electric charge accumulates on the dielectric surface, and the microdischarge disappears. Thus, the electric barrier discharge is a discharge in which micro discharge spreads over the entire tube wall and is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless field discharge can be used in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro-discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through to extract light to the outside in order to discharge in the entire discharge space. Must. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

  In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are arranged in close contact, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution. The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. Therefore, a very inexpensive light source can be provided.

  Since the double cylindrical lamp is processed by closing both ends of the inner and outer tubes, it is more likely to be damaged during handling and transportation than a thin tube lamp. Further, the outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As for the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

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

  Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, light having a long wavelength that causes a temperature rise due to light is not emitted, and energy is irradiated at a single wavelength in the ultraviolet region, so that the rise in the surface temperature of the object to be fired is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  In the present invention, it is preferable that the polysilazane modified layer includes a polysilazane modified portion and an unmodified portion by vacuum ultraviolet irradiation treatment.

By forming the polysilazane modified layer having such two parts, the polysilazane modified part is continuously changed from the vacuum ultraviolet irradiation side to the densely formed part. Since there is no interface, smooth heat conduction is possible in heat transfer. Further, in the present invention, since the electrode is formed on the dense modified portion side, unevenness due to damage at the time of electrode formation is difficult to be formed, and unevenness of heat conversion due to the unevenness is also eliminated. It is preferred that it be formed. Further, the inside can be converted into a ceramic by SiO ₂ conversion with oxygen in the coating environment as an unmodified site, and a high gas barrier property can be imparted.

  In the modification treatment by the vacuum ultraviolet irradiation treatment, the reaction proceeds quickly on the surface of the coating layer, and thus the distribution state of the modified portion and the unmodified portion as described above can be created by adjusting the vacuum ultraviolet irradiation conditions. It is.

<Method for confirming reformed and unmodified parts>
In the present invention, the modified portion and the unmodified portion formed by the modification treatment of polysilazane can be confirmed by observation of the cross section of the layer with a transmission electron microscope (TEM).

(Section TEM observation)
The film sample is sliced by the following high performance focused ion beam (FIB) processing apparatus, and then subjected to cross-sectional TEM observation. At this time, if the sample is continuously irradiated with the electron beam, a contrast difference appears between a portion that is damaged by the electron beam and a portion that is not. The modified part according to the present invention is not easily damaged by electron beam because it is densified by the modification process, but the other part is damaged by the electron beam and the deterioration is confirmed. Through the cross-sectional TEM observation confirmed in this way, the film thicknesses of the modified portion and the unmodified portion can be calculated.
(FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
Electron beam irradiation time: 5 to 60 seconds (Smoothness: surface roughness Ra)
The surface roughness (Ra) of the polysilazane modified layer 11 is preferably 2 nm or less, and more preferably 1 nm or less. When the surface roughness is in the above range, when using a resin base material for organic EL elements, the light transmission efficiency is improved by a smooth film surface with less unevenness, and the energy conversion efficiency is reduced by the leakage current between electrodes. Is preferable. The surface roughness (Ra) of the polysilazane modified layer 11 can be measured by the following method.

(Surface roughness measurement method; AFM measurement)
The surface roughness is calculated from an uneven sectional curve continuously measured with an AFM (Atomic Force Microscope), for example, DI3100 manufactured by Digital Instruments, with a detector having a stylus with a minimum tip radius. This is a roughness related to the amplitude of fine irregularities measured by a stylus many times in a section whose measurement direction is several tens of μm.

(3) Resin substrate The resin substrate according to the present invention is preferably a resin film in consideration of productivity such as roll-to-roll.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, 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) Is mentioned.

As described above, a film made of an inorganic material or an organic material, or a hybrid film combining these films may be formed on the surface of the resin film. Such coatings and hybrid coatings have a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS K 7129-1992, 0.01 g / m ² · 24 h. The following gas barrier film (also referred to as a gas barrier film or the like) is preferable. Furthermore, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / m ² · A high gas barrier layer of 24 hours or less is preferable. The material for forming the gas barrier layer as described above may be any material that has a function of suppressing intrusion of factors that cause deterioration of electronic devices such as moisture and oxygen and organic EL elements. For example, silicon oxide, Silicon, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the gas barrier layer, it is more preferable to have a laminated structure of a layer made of these non-base materials (inorganic layer) and a layer made of a base material (organic layer). Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  There are no particular limitations on the method for producing a resin film having a gas barrier layer (gas barrier film). For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method The plasma polymerization method, the atmospheric pressure plasma polymerization method, the plasma CVD method, the laser CVD method, the thermal CVD method, the coating method, etc. can be used, but the atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is used. Is particularly preferred.

(Gas barrier layer: composition)
The gas barrier layer 27 is preferably composed of an inorganic film having a refractive index distribution in the thickness direction and having one or more extreme values in the refractive index distribution. The gas barrier layer 27 is made of a material containing silicon, oxygen, and carbon, and has a laminated structure including a plurality of layers having different silicon, oxygen, and carbon contents.

  The gas barrier layer 27 has a ratio (atomic ratio) between the distance from the surface of the gas barrier layer 27 (interface of the polysilazane modified layer 11) in the film thickness direction and the atomic weight of each of the elements (silicon, oxygen, or carbon). Each element has a characteristic distribution curve.

  In addition, the atomic ratio of silicon, oxygen, or carbon is represented by the ratio [(Si, O, C) / (Si + O + C)] of silicon, oxygen, or carbon to the total amount of each element of silicon, oxygen, and carbon.

  The silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve indicate the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon at a distance from the surface of the gas barrier layer 27. Further, a distribution curve showing the relationship between the distance from the surface of the gas barrier layer 27 (interface of the polysilazane modified layer 11) in the film thickness direction and the ratio (atomic ratio) of the total atomic weight of oxygen and carbon is expressed as oxygen. The carbon distribution curve.

The gas barrier layer 27 may further contain nitrogen in addition to silicon, oxygen and carbon. By containing nitrogen, the refractive index of the gas barrier layer 27 can be controlled. For example, the refractive index of SiO ₂ is 1.5, whereas the refractive index of SiN is about 1.8 to 2.0. For this reason, the gas barrier layer 27 contains nitrogen. By forming SiON in the gas barrier layer 27, a preferable refractive index value of 1.6 to 1.8 can be obtained. Thus, the refractive index of the gas barrier layer 27 can be controlled by adjusting the nitrogen content.

  When the gas barrier layer 27 contains nitrogen, the distribution curve of each element (silicon, oxygen, carbon, or nitrogen) constituting the gas barrier layer 27 is as follows.

  In the case of containing nitrogen in addition to silicon, oxygen and carbon, the atomic ratio of silicon, oxygen, carbon or nitrogen is the ratio of silicon, oxygen, carbon or nitrogen to the total amount of each element of silicon, oxygen, carbon and nitrogen [(Si, O, C, N) / (Si + O + C + N)].

  The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve represent the atomic ratio of silicon, the atomic ratio of oxygen, the atomic ratio of carbon, and the nitrogen atoms at a distance from the surface of the gas barrier layer 27, respectively. Indicates the ratio.

(Relationship between element distribution curve and refractive index distribution)
The refractive index distribution of the gas barrier layer 27 can be controlled by the amount of carbon and the amount of oxygen in the thickness direction of the gas barrier layer 27.

  FIG. 2 shows an example of the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve of the gas barrier layer 27. 3 shows an enlarged carbon distribution curve from the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve shown in FIG. 2 and 3, the horizontal axis represents the distance [nm] from the surface of the gas barrier layer 27 in the film thickness direction. The vertical axis represents the atomic ratio [at%] of silicon, oxygen, carbon, or nitrogen with respect to the total amount of each element of silicon, oxygen, and carbon.

  In addition, the detail of the measuring method of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve is mentioned later.

  As shown in FIG. 2, the atomic ratio of silicon, oxygen, carbon, and nitrogen changes depending on the distance from the surface of the gas barrier layer 27. In particular, for oxygen and carbon, the atomic ratio varies greatly depending on the distance from the surface of the gas barrier layer 27, and each distribution curve has a plurality of extreme values. In addition, the oxygen distribution curve and the carbon distribution curve are correlated, and the oxygen atomic ratio decreases at a distance where the carbon atomic ratio is large, and the oxygen atomic ratio increases at a distance where the carbon atomic ratio is small.

  FIG. 4 shows a refractive index distribution curve of the gas barrier layer 27. In FIG. 4, the horizontal axis indicates the distance [nm] from the surface of the gas barrier layer 27 in the film thickness direction. The vertical axis represents the refractive index of the gas barrier layer 27. The refractive index of the gas barrier layer 27 shown in FIG. 4 is a measured value of the distance from the surface of the gas barrier layer 27 in the film thickness direction and the refractive index of the gas barrier layer 27 with respect to visible light at this distance. The refractive index distribution of the gas barrier layer 27 can be measured using a known method, for example, a spectroscopic ellipsometer (ELC-300 manufactured by JASCO Corporation) or the like.

  As shown in FIGS. 3 and 4, there is a correlation between the atomic ratio of carbon and the refractive index of the gas barrier layer 27. Specifically, in the gas barrier layer 27, the refractive index of the gas barrier layer 27 increases at a position where the atomic ratio of carbon increases. Thus, the refractive index of the gas barrier layer 27 changes according to the atomic ratio of carbon. That is, in the gas barrier layer 27, the refractive index distribution curve of the gas barrier layer 27 can be controlled by adjusting the distribution of the atomic ratio of carbon in the film thickness direction.

  Since the carbon atomic ratio and the oxygen atomic ratio are also correlated as described above, the refractive index distribution curve of the gas barrier layer 27 is controlled by controlling the oxygen atomic ratio and the distribution curve. be able to.

  By providing the gas barrier layer 27 having an extreme value in the refractive index distribution, reflection and interference occurring at the interface of the resin base material 26 can be suppressed. For this reason, the light transmitted through the first electrode 25 is emitted without being affected by total reflection or interference by the action of the gas barrier layer 27. Therefore, the light quantity is not reduced, and the light extraction efficiency of the first electrode 25 is improved.

  In addition, when a metal transparent conductive layer made of silver or the like is used as the conductive layer 12, the light transmitted through the first electrode 25 is reflected or interfered with the conductive layer 12, thereby causing a large viewing angle dependency problem. Cheap. This is thought to be due to the aggregation of the metal in the metal transparent conductive layer or the reflection of a specific wavelength region at the metal transparent conductive layer or its interface to interfere with the emission spectrum, and the emission spectrum changes to show viewing angle dependence. ing.

  Therefore, the viewing angle dependency can be suppressed by adjusting the refractive index distribution of the gas barrier layer 27 so as not to interfere with a specific wavelength of the emitted light. The refractive index distribution of the gas barrier layer 27 can be controlled by the atomic ratio of carbon. For this reason, by controlling the carbon distribution curve, it is possible to impart arbitrary optical characteristics to the gas barrier layer 27.

  In this example, the gas barrier layer 27 has one or more extreme values in the refractive index distribution curve, so that the color gamut can be adjusted by controlling the light spectrum. For this reason, it is possible to disperse the interference conditions of the first electrode 25 and to prevent interference at a specific wavelength. Therefore, the light distribution property of the light transmitted through the first electrode 25 is controlled by the gas barrier layer 27, and the viewing angle dependency of the emission spectrum is eliminated, thereby realizing the uniform light distribution property of the first electrode 25. it can.

(Conditions for each element's distribution curve)
In the gas barrier layer 27, the atomic ratio of silicon, oxygen and carbon, or the distribution curve of each element preferably satisfies the following conditions (i) to (iii).
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the gas barrier layer 27, the following formula (1):
(Atomic ratio of carbon) <(Atomic ratio of silicon) <(Atomic ratio of oxygen) (1)
The condition represented by is satisfied.

Alternatively, in a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the gas barrier layer 27, the following formula (2):
(Atomic ratio of oxygen) <(atomic ratio of silicon) <(atomic ratio of carbon) (2)
The condition represented by is satisfied.
(Ii) The carbon distribution curve has at least one local maximum and local minimum.
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

  The first electrode 25 preferably includes a gas barrier layer 27 that satisfies at least one of the above conditions (i) to (iii). In particular, it is preferable to provide a gas barrier layer 27 that satisfies all of the above conditions (i) to (iii). Further, two or more gas barrier layers 27 satisfying all the above conditions (i) to (iii) may be provided. When two or more gas barrier layers 27 are provided, the materials of the plurality of thin film layers may be the same or different. When two or more gas barrier layers 27 are provided, the gas barrier layer 27 may be formed on one surface of the resin base material 26, or may be formed on both surfaces of the resin base material 26. Good.

  The refractive index of the gas barrier layer 27 can be controlled by the atomic ratio of carbon or oxygen as in the correlation shown in FIGS. For this reason, the refractive index of the gas barrier layer 27 can be adjusted to a preferable range by the above conditions (i) to (iii).

(Carbon distribution curve)
The gas barrier layer 27 needs to have at least one extreme value in the carbon distribution curve. In such a gas barrier layer 27, it is more preferable that the carbon distribution curve has at least two extreme values, and it is even more preferable that the carbon distribution curve has at least three extreme values. Furthermore, it is preferable that the carbon distribution curve has at least one maximum value and one minimum value.

  When the carbon distribution curve has no extreme value, the light distribution of the obtained gas barrier layer 27 is insufficient. For this reason, it becomes difficult to eliminate the light angle dependency of the first electrode 25 obtained through the conductive layer 12.

  When the gas barrier layer 27 has three or more extreme values, one extreme value of the carbon distribution curve and another extreme value adjacent to the extreme value are obtained from the surface of the gas barrier layer 27. The difference in the distance in the film thickness direction is preferably 200 nm or less, and more preferably 100 nm or less.

(Extreme value)
In the gas barrier layer 27, the extreme value of the distribution curve corresponds to the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer 27 in the film thickness direction of the gas barrier layer 27, or the value thereof. The measured value of the refractive index distribution curve.

  In the gas barrier layer 27, the maximum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer 27 is changed. Moreover, from this point, the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer 27 is further changed by 20 nm is reduced by 3 at% or more.

  In the gas barrier layer 27, the minimum value of the distribution curve of each element is that the value of the atomic ratio of the element changes from decrease to increase when the distance from the surface of the gas barrier layer 27 is changed. In addition, from this point, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer 27 is further changed by 20 nm is increased by 3 at% or more.

  In the carbon distribution curve of the gas barrier layer 27, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is preferably 5 at% or more. In such a gas barrier layer 27, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and further preferably 7 at% or more. When the difference between the maximum value and the minimum value of the atomic ratio of carbon is less than the above range, the refractive index difference in the refractive index distribution curve of the obtained gas barrier layer 27 becomes small, and the light distribution becomes insufficient.

  There is a correlation between the amount of carbon distribution and the refractive index, and when the absolute value of the maximum value and the minimum value of the preferable carbon atom is 7 at% or more, the absolute value of the difference between the maximum value and the minimum value of the obtained refractive index is It becomes 0.2 or more.

(Oxygen distribution curve)
The gas barrier layer 27 preferably has at least one extreme value in the oxygen distribution curve. In particular, the gas barrier layer 27 preferably has an oxygen distribution curve having at least two extreme values, and more preferably has at least three extreme values. Furthermore, it is preferable that the oxygen distribution curve has at least one maximum value and one minimum value.

  When the oxygen distribution curve has no extreme value, the light distribution of the obtained gas barrier layer 27 becomes insufficient. For this reason, it becomes difficult to eliminate the light angle dependency of the first electrode 25 obtained through the conductive layer 12.

  When the gas barrier layer 27 has three or more extreme values, one extreme value of the oxygen distribution curve and another extreme value adjacent to the extreme value are obtained from the surface of the gas barrier layer 27. The difference in the distance in the film thickness direction is preferably 200 nm or less, and more preferably 100 nm or less. In the oxygen distribution curve of the gas barrier layer 27, the absolute value of the difference between the maximum value and the minimum value of the oxygen atomic ratio is preferably 5 at% or more. In such a gas barrier layer 27, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen is more preferably 6 at% or more, and further preferably 7 at% or more. If the difference between the maximum value and the minimum value of the atomic ratio of oxygen is less than the above range, light distribution is insufficient from the refractive index distribution curve of the obtained gas barrier layer 27.

(Silicon distribution curve)
The gas barrier layer 27 preferably has an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of less than 5 at%. In such a gas barrier layer 27, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon is more preferably less than 4 at%, and further preferably less than 3 at%. When the difference between the maximum value and the minimum value of the atomic ratio of silicon is not less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained gas barrier layer 27.

(Total amount of oxygen and carbon: oxygen carbon distribution curve)
In the gas barrier layer 27, the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms is defined as an oxygen-carbon distribution curve.

  The gas barrier layer 27 preferably has an absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen-carbon distribution curve of less than 5 at%, more preferably less than 4 at%. Preferably, it is particularly preferably less than 3 at%.

  When the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon is not less than the above range, the light distribution is insufficient from the refractive index distribution curve of the obtained gas barrier layer 27.

(XPS depth profile)
The silicon distribution curve, oxygen distribution curve, carbon distribution curve, oxygen carbon distribution curve, and nitrogen distribution curve described above are measured by X-ray photoelectron spectroscopy (XPS), rare gas ion sputtering such as argon, and the like. By using together, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).

  In the element distribution curve with the horizontal axis as the etching time, the etching time generally correlates with the distance from the surface of the gas barrier layer 27 in the film thickness direction. For this reason, when measuring the XPS depth profile, the distance from the surface of the gas barrier layer 27 calculated from the relationship between the etching rate and the etching time is defined as “the distance from the surface of the gas barrier layer 27 in the film thickness direction”. Can be adopted.

For XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and an etching rate (etching rate) is set to 0.05 nm / sec (SiO ₂ thermal oxide film equivalent value). It is preferable to do.

  Further, the gas barrier layer 27 is formed in a film surface direction (a direction parallel to the surface of the gas barrier layer 27) from the viewpoint of forming a layer having a uniform and excellent light distribution on the entire film surface. Is substantially uniform. The fact that the gas barrier layer 27 is substantially uniform in the film surface direction means that the number of extreme values of the element distribution curves at the respective measurement points is the same at any two points on the film surface of the gas barrier layer 27. And the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the distribution curve is the same as each other, or the difference between the maximum value and the minimum value is within 5 at%.

(Substantially continuous)
In the gas barrier layer 27, the carbon distribution curve is preferably substantially continuous. The carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the distance (x, unit: nm) from the surface of the gas barrier layer 27 calculated from the etching rate and etching time, and the atomic ratio of carbon (C, unit: at%) are expressed by the following formulas. (F1):
(DC / dx) ≦ 0.5 (F1)
The condition represented by is satisfied.

(Silicon atomic ratio, oxygen atomic ratio)
In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, the above formula (F1) is used when the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio are 90% or more of the film thickness of the gas barrier layer 27. It is preferable that the condition represented by In this case, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 27 is preferably 25 to 45 at%, and 30 to 40 at%. It is more preferable.

  The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer 27 is preferably 33 to 67 at%, and more preferably 45 to 67 at%. preferable.

  Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer 27 is preferably 3 to 33 at%, and more preferably 3 to 25 at%. preferable.

(Thickness of thin film layer)
The thickness of the gas barrier layer 27 is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 100 to 1000 nm. When the thickness of the gas barrier layer 27 is out of the above range, the light distribution of the gas barrier layer 27 becomes insufficient.

  When the gas barrier layer 27 is formed from a plurality of layers, the total thickness of the gas barrier layer 27 is in the range of 10 to 10,000 nm, preferably in the range of 10 to 5000 nm, and preferably in the range of 100 to 3000 nm. The range is more preferable, and the range of 200 to 2000 nm is particularly preferable.

(Primer layer)
The gas barrier layer 27 may include a primer coat layer, a heat-sealable resin layer, an adhesive layer, and the like between the resin base material 26. The primer coat layer can be formed using a known primer coat agent that can improve the adhesion between the resin base material 26 and the gas barrier layer 27. Moreover, a heat-sealable resin layer can be suitably formed using well-known heat-sealable resin. Furthermore, the adhesive layer can be appropriately formed using a known adhesive, and a plurality of gas barrier layers 27 may be adhered by such an adhesive layer.

(Gas barrier layer manufacturing method)
The gas barrier layer 27 is preferably a layer formed by plasma enhanced chemical vapor deposition. As the gas barrier layer 27 formed by the plasma chemical vapor deposition method, a plasma chemical vapor is generated in which a resin base material 26 is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers. A layer formed by a phase growth method (plasma CVD) is more preferable. The plasma enhanced chemical vapor deposition method may be a plasma chemical vapor deposition method using a Penning discharge plasma method. Moreover, when discharging between a pair of film-forming rollers, it is preferable to reverse the polarity of a pair of film-forming rollers alternately.

  When generating plasma in the plasma chemical vapor deposition method, it is preferable to generate plasma discharge in the space between the plurality of film forming rollers. In particular, it is more preferable to use a pair of film forming rollers, dispose the resin base material 26 on each of the pair of film forming rollers, and generate plasma by discharging between the pair of film forming rollers.

  In this manner, the resin base material 26 is disposed on the pair of film forming rollers, and a film is formed on the resin base material 26 existing on one film forming roller by discharging between the film forming rollers. be able to. At the same time, it is possible to form a film on the resin substrate 26 on the other film forming roller. For this reason, the film-forming rate can be doubled and a thin film can be manufactured efficiently. Furthermore, a film having the same structure can be formed on each resin substrate 26 on the pair of film forming rollers.

  In the plasma chemical vapor deposition method, a film forming gas containing an organosilicon compound and oxygen is preferably used. The oxygen content in the film forming gas is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas.

  The gas barrier layer 27 is preferably a layer formed by a continuous film forming process.

(Gas barrier layer manufacturing equipment)
As described above, the gas barrier layer 27 is preferably formed on the surface of the resin base material 26 by a roll-to-roll method from the viewpoint of productivity. An apparatus capable of producing the gas barrier layer 27 by plasma chemical vapor deposition is not particularly limited, but includes at least a pair of film forming rollers and a plasma power source, and can discharge between the film forming rollers. It is preferable that the device is configured.

  For example, when the manufacturing apparatus 30 shown in FIG. 5 is used, it is also possible to manufacture by a roll-to-roll method using a plasma chemical vapor deposition method. Hereinafter, the manufacturing method of the gas barrier layer 27 will be described with reference to FIG. FIG. 5 is a schematic diagram showing an example of a manufacturing apparatus suitable for manufacturing the gas barrier layer 27.

  The manufacturing apparatus 30 shown in FIG. 5 includes a delivery roll 31, transport rollers 32, 33, 34, 35, film formation rollers 36, 37, a gas supply pipe 38, a plasma generation power source 39, and a film formation roller 36. And 37, and magnetic field generators 41 and 42 installed inside 37, and a winding roll 43. In the manufacturing apparatus 30, at least film forming rollers 36 and 37, a gas supply pipe 38, a plasma generating power source 39, and magnetic field generating apparatuses 41 and 42 are disposed in a vacuum chamber (not shown). Furthermore, in the manufacturing apparatus 30, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be adjusted by the vacuum pump.

  In the manufacturing apparatus 30, each film-forming roller has a plasma generation power supply 39 so that the pair of film-forming rollers (the film-forming roller 36 and the film-forming roller 37) can function as a pair of second electrodes. It is connected to the. For this reason, in the manufacturing apparatus 30, it is possible to discharge to the space between the film formation roller 36 and the film formation roller 37 by supplying electric power from the power source 39 for plasma generation. Plasma can be generated in a space between the film forming roller 37 and the film forming roller 37. In addition, when using the film-forming roller 36 and the film-forming roller 37 as electrodes, the material and design of the film-forming roller 36 and the film-forming roller 37 may be changed so that they can also be used as electrodes. In the manufacturing apparatus 30, the pair of film forming rollers (film forming rollers 36 and 37) are preferably arranged such that the central axes are substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 36 and 37), the film forming rate can be doubled and a film having the same structure can be formed. For this reason, it is possible to at least double the extreme value in the carbon distribution curve. And according to the manufacturing apparatus 30, it is possible to form the gas barrier layer 27 on the surface of the film 40 by the CVD method, while depositing a film component on the surface of the film 40 on the film forming roller 36, Furthermore, since the film component can be deposited on the surface of the film 40 also on the film forming roller 37, the gas barrier layer 27 can be efficiently formed on the surface of the film 40.

  Further, inside the film forming roller 36 and the film forming roller 37, magnetic field generators 41 and 42 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  Furthermore, as the film forming roller 36 and the film forming roller 37, known rollers can be used. As the film forming rollers 36 and 37, it is preferable to use rollers having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rollers 36 and 37 are preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in the manufacturing apparatus 30, the film 40 is arrange | positioned on a pair of film-forming roller (The film-forming roller 36 and the film-forming roller 37) so that the surface of the film 40 may respectively oppose. By disposing the film 40 in this way, each surface of the film 40 existing between the pair of film forming rollers when generating a plasma by discharging between the film forming roller 36 and the film forming roller 37. At the same time, the gas barrier layer 27 can be formed. That is, according to the manufacturing apparatus 30, the film component can be deposited on the surface of the film 40 on the film formation roller 36 and further the film component can be deposited on the film formation roller 37 by the CVD method. The gas barrier layer 27 can be efficiently formed on the surface of the film 40.

  Moreover, a well-known roller can be used as the sending roll 31 and the conveyance rollers 32, 33, 34, and 35 used for the manufacturing apparatus 30. The winding roll 43 is not particularly limited as long as it can wind the film 40 on which the gas barrier layer 27 is formed, and a known roller can be used.

  As the gas supply pipe 38, a pipe capable of supplying or discharging the raw material gas at a predetermined speed can be used. Further, as the plasma generation power source 39, a power source of a known plasma generation apparatus can be used. The plasma generating power source 39 supplies power to the film forming rollers 36 and 37 connected thereto, and enables the film forming rollers 36 and 37 to be used as a second electrode for discharging. As the plasma generating power source 39, it is preferable to use an AC power source or the like capable of alternately reversing the polarity of the film forming roller, because it is possible to perform plasma CVD more efficiently. In addition, since it becomes possible to perform plasma CVD more efficiently, the power source 39 for plasma generation that can set the applied power to 100 W to 10 kW and set the AC frequency to 50 Hz to 500 kHz is provided. More preferably, it is used. As the magnetic field generators 41 and 42, known magnetic field generators can be used. Furthermore, as the film 40, the resin base material 26 in which the gas barrier layer 27 is formed in advance can be used in addition to the resin base material 26 applicable to the first electrode 25 described above. Thus, the thickness of the gas barrier layer 27 can be increased by using the resin base material 26 on which the gas barrier layer 27 is formed in advance as the film 40.

  As described above, using the manufacturing apparatus 30 shown in FIG. 5, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film conveyance speed By adjusting the gas barrier layer 27, the gas barrier layer 27 can be manufactured. That is, by using the manufacturing apparatus 30 shown in FIG. 5 and discharging a film forming gas (raw material gas or the like) between the pair of film forming rollers (film forming rollers 36 and 37) while supplying it into the vacuum chamber, A deposition gas (such as a source gas) is decomposed by plasma, and a gas barrier layer 27 is formed on the surface of the film 40 on the deposition roller 36 and on the surface of the film 40 on the deposition roller 37 by a plasma CVD method. The During film formation, the film 40 is conveyed by the delivery roll 31 and the film formation roller 36, respectively, so that a gas barrier is formed on the surface of the film 40 by a roll-to-roll continuous film formation process. Layer 27 is formed.

(Raw material gas)
The source gas in the film forming gas used for forming the gas barrier layer 27 can be appropriately selected and used depending on the material of the gas barrier layer 27 to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used. Examples of organosilicon compounds include hexamethyldisiloxane, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propyl. Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1.1.3.3-tetramethyldisiloxane are used from the viewpoints of characteristics such as film formation and light distribution of the gas barrier layer 27 obtained. It is preferable. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As the carrier gas and the discharge gas, a known gas can be used. For example, a rare gas such as helium, argon, neon, or xenon, or hydrogen can be used.

  When the film forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the amount of the reactive gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessively higher than the ratio of. If the ratio of the reaction gas is excessive, the light distribution of the gas barrier layer 27 cannot be obtained sufficiently. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

Hereinafter, as an example, a case where hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) is used as a source gas and oxygen (O ₂ ) is used as a reaction gas will be described.

When a silicon-oxygen-based thin film is produced by reacting a film-forming gas containing hexamethyldisiloxane as a source gas and oxygen as a reaction gas by plasma CVD, the following reaction formula (1):
_{(CH 3) 6 Si 2 O} + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2 ··· (1)
The following reaction occurs and silicon dioxide is produced. In this reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. For this reason, when 12 mol or more of oxygen is contained in 1 mol of hexamethyldisiloxane in the film forming gas and completely reacted, a uniform silicon dioxide film is formed. For this reason, the incomplete reaction is performed by controlling the gas flow rate ratio of the raw material to a flow rate equal to or lower than the theoretical reaction raw material ratio. That is, it is necessary to make the amount of oxygen less than 12 moles of the stoichiometric ratio per mole of hexamethyldisiloxane.

  In the actual reaction in the plasma CVD chamber, since the raw material hexamethyldisiloxane and the reactive gas oxygen are supplied from the gas supply unit to the film formation region, the molar amount (flow rate) of the reactive gas oxygen is the raw material. Even if the molar amount (flow rate) is 12 times the molar amount (flow rate) of hexamethyldisiloxane, the reaction cannot actually proceed completely. That is, it is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material.

  For this reason, it is preferable that the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer 27, and the desired gas barrier layer 27. Can be formed.

  If the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer 27. Therefore, the transparency of the gas barrier layer 27 is lowered. For this reason, like the 1st electrode 25, it will become impossible to utilize for the board | substrate which has the transparency required transparency. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

(Degree of vacuum)
Although the pressure (degree of vacuum) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-100 Pa.

(Deposition roller)
In the plasma CVD method described above, the electric power applied to the electrode drum connected to the plasma generating power source 39 for discharging between the film forming rollers 36 and 37 depends on the type of source gas, the pressure in the vacuum chamber, and the like. Can be adjusted accordingly. For example, a range of 0.1 to 10 kW is preferable. If the applied power is less than the lower limit, particles tend to be generated. On the other hand, if the upper limit is exceeded, the amount of heat generated during film formation increases, the temperature of the substrate surface during film formation rises, the resin base material 26 loses heat, and wrinkles occur during film formation.

  In this example, the electrode drum is installed on the film forming rollers 36 and 37.

  The conveyance speed (line speed) of the film 40 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, and the like, but is preferably in the range of 0.25 to 100 m / min. A range of 5 to 20 m / min is more preferable. If the line speed is less than the lower limit, wrinkles due to heat tend to occur in the film. On the other hand, if the line speed exceeds the upper limit, the thickness of the formed gas barrier layer 27 tends to be thin.

(Smooth layer)
A smooth layer may be formed between the resin base material 26 and the gas barrier layer 27. The smooth layer is for flattening the rough surface of the resin base material 26 having protrusions or the like, or by filling the unevenness and pinholes generated in the gas barrier layer 27 with the protrusions existing on the resin base material 26. Provided. Such a smooth layer is basically formed by curing a photosensitive resin.

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

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with acrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or as a mixture with another compound.

  The photosensitive resin composition contains a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  The smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used in order to improve the film formability and prevent the generation of pinholes in the film.

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

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. When the thickness is smaller than 10 nm, the coating property may be impaired when the coating means comes into contact with the surface of the smooth layer in the step of applying a silicon compound described later by a coating method such as a wire bar or a wireless bar. Moreover, when larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

  The surface roughness is a roughness related to the amplitude of fine irregularities measured using an AFM (atomic force microscope). This surface roughness is calculated from the cross-sectional curve of the unevenness measured continuously by measuring a number of times within several tens of μm with a detector having a stylus having a minimum tip radius of AFM.

(Additive to smooth layer)
The smooth layer may contain an additive. The additive contained in the smooth layer is preferably reactive silica particles in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin (hereinafter also simply referred to as “reactive silica particles”).

  Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin preferably contains a compound capable of undergoing a photopolymerization reaction with the photosensitive group introduced on the surface of the reactive silica particles, for example, an unsaturated organic compound having a polymerizable unsaturated group. The photosensitive resin may have a solid content adjusted by mixing a general-purpose diluent solvent with reactive silica particles or an unsaturated organic compound having a polymerizable unsaturated group.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By using the average particle size in the above range, when used in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later, a smooth layer having both optical properties such as light distribution and hard coat properties. It becomes easy to form.

  In order to make it easier to obtain the above effect, the average particle diameter is preferably in the range of 0.001 to 0.01 μm. The smooth layer preferably contains the above inorganic particles in a mass ratio of 20% to 60%. By adding 20% or more, the adhesion between the resin base material 26 and the gas barrier layer 27 is improved. On the other hand, if it exceeds 60%, the film may be bent, cracks may be generated when heat treatment is performed, and optical properties such as transparency and refractive index of the gas barrier layer 27 may be affected.

  In this example, as the reactive silica particles, a hydrolyzable silyl group is hydrolyzed to form a silyloxy group between the silica particles and chemically bonded to the polymerizable unsaturated group modified hydrolyzable. Silane can be used.

  Examples of the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  The thickness of the smooth layer is preferably 1 to 10 μm, more preferably 2 to 7 μm. By setting it to 1 μm or more, the smoothness of the resin base material 26 having a smooth layer becomes sufficient. Moreover, by making it 10 μm or less, it becomes easy to adjust the balance of optical characteristics, and it is possible to easily suppress curling when the smooth layer is provided only on one surface of the resin base material 26.

  The smooth layer may contain a matting agent as another additive. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the smooth layer. It is preferable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

(Bleed-out prevention layer)
The gas barrier layer 27 can be provided with a bleed-out prevention layer. When the film-like resin base material 26 having a smooth layer is heated, the bleed-out prevention layer contaminates the surface of the resin base material 26 by transferring unreacted oligomers and the like from the resin base material 26 to the surface. In order to suppress the phenomenon, it is provided on the opposite surface of the substrate having a smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  As the bleed-out preventing layer, an unsaturated organic compound having a polymerizable unsaturated group can be used. As this unsaturated organic compound, a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, a unit price unsaturated organic compound having one polymerizable unsaturated group in the molecule, or the like Is preferably used.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolprop Tetra (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  The bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like.

  Examples of this thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Acetal resins such as vinyl resins, polyvinyl formal, polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, etc. Is mentioned.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.

  In addition, ionizing radiation curable resins are cured by irradiating ionizing radiation (ultraviolet rays or electron beams) to ionizing radiation curable paints in which one or more of photopolymerizable prepolymers or photopolymerizable monomers are mixed. Can be made. Here, the photopolymerizable prepolymer is particularly preferably an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing. As the acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. As the photopolymerizable monomer, the above polyunsaturated organic compounds can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like. The bleed-out prevention layer is prepared by blending a matting agent and other necessary components, and then preparing a coating solution with a diluting solvent as necessary, and applying the coating solution to the substrate surface by a conventionally known coating method. It can be formed by irradiating the liquid with ionizing radiation and curing it. In addition, as ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated. Alternatively, an electron beam having a wavelength region of 100 nm or less emitted from a scanning type or curtain type electron beam accelerator is irradiated.

  The thickness of the bleed-out prevention layer is preferably 1 to 10 μm, and particularly preferably 2 to 7 μm. Heat resistance can be sufficiently achieved by setting the thickness to 1 μm or more. Further, by adjusting the thickness to 10 μm or less, it becomes easy to adjust the balance of optical characteristics, and curling when a smooth layer is provided on one surface of the resin base material 26 can be suppressed.

(4) First electrode and second electrode Both the first electrode and the second electrode according to the present invention are transparent electrodes. Here, “transparent” means that the light transmittance at a light wavelength of 550 nm is 50% or more.

As a group of materials that can be used for the first electrode and the second electrode, all electrodes that can be normally used for organic EL elements can be used. Specifically, aluminum, silver, magnesium, lithium, magnesium / same mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO (indium tin oxide ( Indium Tin Oxide (ITO)), ZnO, TiO ₂ , SnO _{2 and} other oxide semiconductors.

  In the present invention, it is preferable that at least one of the first electrode and the second electrode is a layer composed of silver having a thickness of 30 nm or less or an alloy containing silver as a main component.

  When the structure of the first electrode and the second electrode is a layer formed using silver or an alloy containing silver as a main component, at least one kind of atom in which the adjacent layer is selected from a nitrogen atom and a sulfur atom It is preferable that it is a base layer containing the organic compound which has this.

  For example, as shown in FIG. 1, the first electrode 25 preferably has a two-layer structure in which a base layer 23 and an electrode layer 12 formed thereon are sequentially stacked. Among these, the electrode layer 12 is a layer formed using, for example, silver or an alloy containing silver as a main component, and the base layer 23 is, for example, at least one atom selected from nitrogen atoms and sulfur atoms. It is preferable that it is a layer containing the organic compound which has. Although not shown, the same applies to the second electrode layer 46.

  In the first electrode 25, the main component contained in the electrode layer 12 means that the content in the electrode layer 12 is 98% by mass or more.

(4.1) Underlayer The underlayer 23 is a layer serving as a transparent functional layer provided on the transparent substrate 26 side of the electrode layer 12. The material constituting the underlayer 23 is not particularly limited as long as it can suppress the aggregation of silver when forming the electrode layer 12 made of silver or an alloy containing silver as a main component. , Organic compounds having at least one atom selected from a nitrogen atom and a sulfur atom.

  The said organic compound may be 1 type, and may mix 2 or more types. In addition, it is allowed to mix a compound having no nitrogen atom and sulfur atom within a range that does not impair the effect of the underlayer.

  When the underlayer 23 is made of a low refractive index material (refractive index less than 1.7), the upper limit of the layer thickness needs to be less than 50 nm, preferably less than 30 nm, and preferably less than 10 nm. Is more preferable, and it is especially preferable that it is less than 5 nm. By making the layer thickness less than 50 nm, optical loss can be minimized. On the other hand, the lower limit of the layer thickness is required to be 0.05 nm or more, preferably 0.1 nm or more, and particularly preferably 0.3 nm or more. By setting the layer thickness to 0.05 nm or more, the underlayer 23 can be formed uniformly, and the effect (inhibition of silver aggregation) can be made uniform.

  When the underlayer 23 is made of a high refractive index material (refractive index of 1.7 or more), the upper limit of the layer thickness is not particularly limited, and the lower limit of the layer thickness is the same as that of the low refractive index material. is there.

  However, as a simple function of the base layer 23, it is sufficient if the base layer 23 is formed with a necessary layer thickness that allows uniform film formation.

  As a method for forming the underlayer 23, a wet process such as a coating method, an ink jet method, a coating method, or a dip method, or a dry process such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, or the like is used. And the like. Among these, the vapor deposition method is preferably applied.

  Hereinafter, an organic compound having at least one atom selected from a nitrogen atom and a sulfur atom will be described.

(4.1.1) Organic compound having a nitrogen atom The organic compound having a nitrogen atom is preferably a compound having a melting point of 80 ° C or higher and a molecular weight Mw in the range of 150 to 1200, silver or A compound having a large interaction with the silver alloy is preferable, and examples thereof include a nitrogen-containing heterocyclic compound and a phenyl group-substituted amine compound.

The organic compound having a nitrogen atom has an effective unshared electron pair content [n / M] (ratio of the number n of effective unshared electron pairs to the molecular weight M of the organic compound having a nitrogen atom) is 2.0 ×. 10 is a selected compound such that the ^-3 or more, more preferably 3.9 × ^{10 -3} or more.

  Here, the effective unshared electron pair is an unshared electron pair that does not participate in aromaticity and is not coordinated to the metal among the unshared electron pairs of the nitrogen atoms constituting the compound. To do.

  The aromaticity here means an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel rule”, and is included in the π electron system on the ring. Is 4n + 2 (n is an integer of 0 or more).

  The effective unshared electron pair as described above is such that the unshared electron pair possessed by the nitrogen atom is aromatic regardless of whether or not the nitrogen atom itself provided with the unshared electron pair is a heteroatom constituting the aromatic ring. It is selected based on whether or not it is involved in the family. For example, even if a nitrogen atom is a heteroatom constituting an aromatic ring, if the nitrogen atom has an unshared electron pair that does not participate in aromaticity, the unshared electron pair is an effective unshared electron pair. Counted as one of

  In contrast, even if a nitrogen atom is not a heteroatom that constitutes an aromatic ring, if all of the non-shared electron pairs of the nitrogen atom are involved in aromaticity, the nitrogen atom is not shared. An electron pair is not counted as a valid unshared electron pair.

  In each compound, the number n of effective unshared electron pairs coincides with the number of nitrogen atoms having effective unshared electron pairs.

  When the underlayer is composed of an organic compound having a plurality of nitrogen atoms, the effective unshared electron pair content [n / M] is based on the mixing ratio of each compound and the effective molecular weight M of the mixed compound. The number n of unshared electron pairs is calculated, and the ratio of the number n of effective unshared electron pairs to the molecular weight M is defined as the effective unshared electron pair content [n / M], and this value is within the predetermined range described above. It is preferable that

Hereinafter, as the low-molecular organic compound having a nitrogen atom constituting the underlayer, the above-mentioned effective compound number [n / M] is 2.0 × 10 ⁻³ or more as exemplified compound No. 1 to 45 are shown, but the present invention is not particularly limited thereto. In addition, Exemplified Compound No. In 31 copper phthalocyanine, among the unshared electron pairs of nitrogen atoms, the unshared electron pairs of nitrogen atoms not coordinated to copper are counted as effective unshared electron pairs.

上記例示化合物Ｎｏ．１〜４５について、有効非共有電子対の数ｎ、分子量Ｍ及び有効非共有電子対含有率［ｎ／Ｍ］を表１に示す。

The above exemplified compound No. Table 1 shows the number n of effective unshared electron pairs, the molecular weight M, and the effective unshared electron pair content [n / M] for 1 to 45.

（４．１．２）窒素原子を有するポリマー
本発明においては、窒素原子を有する有機化合物として、ポリマーを用いることもできる。

(4.1.2) Polymer having nitrogen atom In the present invention, a polymer may be used as the organic compound having a nitrogen atom.

  The polymer having a nitrogen atom preferably has a weight average molecular weight in the range of 1,000 to 1,000,000.

  The polymer having a nitrogen atom is preferably a polymer having a partial structure represented by the following general formula (P1) or a partial structure represented by the following general formula (P2).

一般式（Ｐ１）中、Ａ^１は、２価の窒素原子含有基を表す。Ｙ^１は、２価の有機基又は結合手を表す。ｎ１は、重量平均分子量が１０００〜１００００００の範囲内となる繰り返し数を表す。

In General Formula (P1), A ¹ represents a divalent nitrogen atom-containing group. Y ¹ represents a divalent organic group or a bond. n1 represents the number of repetitions in which the weight average molecular weight is in the range of 1,000 to 1,000,000.

一般式（Ｐ２）中、Ａ^２は、１価の窒素原子含有基を表す。ｎ２は、１以上の整数を表す。ｎ２は、銀との相互作用性の点から１〜３の整数であることが好ましく、合成容易性の点から１又は２であることがより好ましい。ｎ２が２以上である場合、複数のＡ^２は、それぞれ同一であってもよいし、異なっていてもよい。Ａ^３及びＡ^４は、２価の窒素原子含有基を表す。Ａ^３及びＡ^４は、同一であってもよいし、異なっていてもよい。ｎ３及びｎ４は、それぞれ独立に、０又は１を表す。Ｙ^２は、（ｎ２＋２）価の有機基を表す。ｎ１は、重量平均分子量が１０００〜１００００００の範囲内となる繰り返し数を表す。

In General Formula (P2), A ² represents a monovalent nitrogen atom-containing group. n2 represents an integer of 1 or more. n2 is preferably an integer of 1 to 3 from the viewpoint of interaction with silver, and more preferably 1 or 2 from the viewpoint of ease of synthesis. When n2 is 2 or more, the plurality of A ² may be the same or different. A ³ and A ⁴ represent a divalent nitrogen atom-containing group. A ³ and A ⁴ may be the same or different. n3 and n4 each independently represents 0 or 1. Y ² represents an (n2 + 2) valent organic group. n1 represents the number of repetitions in which the weight average molecular weight is in the range of 1,000 to 1,000,000.

  The polymer having the partial structure represented by the general formula (P1) or (P2) is a homopolymer composed of only a single structural unit derived from the general formula (P1) or (P2). It may be a copolymer (copolymer) composed of only two or more structural units derived from the above general formulas (P1) and / or (P2).

  Further, in addition to the structural unit represented by the general formula (P1) or (P2), the copolymer may be formed by further having another structural unit having no nitrogen atom-containing group.

  When the polymer having a nitrogen atom has another structural unit not having a nitrogen atom-containing group, the content of the monomer derived from the other structural unit has the effect of the polymer having a nitrogen atom according to the present invention. Although it will not restrict | limit especially if it is a grade which is not impaired, Preferably it exists in the range of 10-75 mol% in the monomer derived from all the structural units, More preferably, it exists in the range of 20-50 mol%.

  The terminal of the polymer having the partial structure represented by the general formula (P1) or (P2) is not particularly limited and is appropriately defined depending on the type of raw material (monomer) used. is there.

In the general formula (P2), the monovalent nitrogen atom-containing group represented by A ² is not particularly limited as long as it is an organic group having a nitrogen atom. Examples of such nitrogen atom-containing groups include amino groups, dithiocarbamate groups, thioamide groups, cyano groups (—CN), isonitrile groups (—N ⁺ ≡C ⁻ ), isocyanate groups (—N═C═O). ), A thioisocyanate group (—N═C═S), or a group containing a substituted or unsubstituted nitrogen-containing aromatic ring.

  Although the specific example (PN1-41) of the monomer which comprises the polymer which has a nitrogen atom which concerns on this invention below is shown, it is not specifically limited to this. In addition, the polymer which has a nitrogen atom is comprised by the repeating number of the range from which the monomer shown below becomes a weight average molecular weight 1000-1 million.

本発明に係る窒素原子を有する低分子有機化合物及びポリマーは、公知、周知の方法で合成することができる。

The low molecular organic compound and polymer having a nitrogen atom according to the present invention can be synthesized by a known and well-known method.

(4.1.3) Organic Compound Having Sulfur Atom The organic compound having a sulfur atom according to the present invention has a sulfide bond, disulfide bond, mercapto group, sulfone group, thiocarbonyl bond, etc. in the molecule. . Among these, it is preferable to have a sulfide bond or a mercapto group.

  The organic compound having a sulfur atom is preferably a compound represented by the following general formulas (1) to (4).

一般式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に、置換基を表す。

In general formula (1), R ₁ and R ₂ each independently represent a substituent.

一般式（２）中、Ｒ_３及びＲ_４は、それぞれ独立に、置換基を表す。

In General Formula (2), R ₃ and R ₄ each independently represent a substituent.

一般式（３）中、Ｒ_５は置換基を表す。

In general formula (3), R ₅ represents a substituent.

一般式（４）中、Ｒ_６は置換基を表す。

In general formula (4), R ₆ represents a substituent.

In the general formula (1), examples of the substituent represented by R ₁ and R ₂ include an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group). Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg, vinyl group, allyl group etc.), alkynyl group (eg, Ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group , Azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl Group, biphenylyl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group , A carbolinyl group, a diazacarbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a phthalazinyl group, etc.), a heterocyclic group (for example, a pyrrolidyl group) Imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, , Cyclopentyloxy group, cyclohexyl Ruoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio Groups (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio groups (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxy) Carbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, Ruaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group Etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridyl) Carbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyl) Oxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylamino) Carbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, Dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group) Group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) Group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butyne) Sulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group and the like), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group and the like), amino group (for example, , Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also called piperidinyl group) , 2,2,6,6-tetramethylpiperidinyl group), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (for example, fluoromethyl group, trifluoromethyl group, etc.) , Pentafluoroethylene Group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester group (For example, dihexyl phosphoryl group), phosphite group (for example, diphenylphosphinyl group), phosphono group and the like.

  These substituents may be further substituted with these substituents, or may be linked to each other to form a ring.

In the general formula (2), examples of the substituent represented by R ₃ and R ₄ include the same substituents as the substituents represented by R ₁ and R ₂ in the general formula (1).

In the general formula (3), examples of the substituent represented by R ₅ include the same substituents as the substituents represented by R ₁ and R ₂ in the general formula (1).

In the general formula (4), examples of the substituent represented by R ₆ include the same substituents as the substituents represented by R ₁ and R ₂ in the general formula (1).

  Although the exemplary compounds (1-1) to (4-1) of organic compounds having a sulfur atom constituting the underlayer are shown below, they are not particularly limited thereto.

（４．１．４）硫黄原子を有するポリマー
本発明においては、硫黄原子を有する有機化合物として、ポリマーを用いることもできる。

(4.1.4) Polymer having a sulfur atom In the present invention, a polymer may be used as the organic compound having a sulfur atom.

  The polymer having a sulfur atom preferably has a weight average molecular weight in the range of 1,000 to 1,000,000.

  Although the specific example (PS1-14) of the monomer which comprises the polymer which has a sulfur atom below is shown, it is not specifically limited to this.

上記したモノマー単位からなるポリマーの重量平均分子量を表２に示す。In addition, the polymer which has a sulfur atom is comprised by the repeating number of the range from which the monomer shown below becomes a weight average molecular weight 1000-1 million. In addition, the numerical values added outside the parentheses represent the constituent ratio (also referred to as molar ratio or composition ratio) of each monomer unit.

Table 2 shows the weight average molecular weight of the polymer comprising the above monomer units.

本発明に用いられる硫黄原子を有する有機化合物及びポリマーは、公知、周知の方法で合成することができる。

The organic compound and polymer having a sulfur atom used in the present invention can be synthesized by known and well-known methods.

In addition, the weight average molecular weight of the polymer which has a nitrogen atom or sulfur atom used for this invention is the value which measured on the following measurement conditions under room temperature (25 degreeC).
(Measurement condition)
Equipment: Tosoh High Speed GPC Equipment HLC-8220GPC
Column: TOSOH TSKgel Super HM-M
Detector: RI and / or UV
Eluent flow rate: 0.6 ml / min Temperature: 30 ° C
Sample concentration: 0.1% by mass
Sample volume: 100 μl
Calibration curve: Prepared with standard polystyrene (standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 500 to 1000000 using 13 samples to create a calibration curve (also referred to as calibration curve) (This was used to calculate the weight average molecular weight. Here, the weight average molecular weight of the polystyrene used in the sample was set at approximately equal intervals.)
(4.2) Electrode Layer The electrode layer 12 is a layer formed using silver or an alloy containing silver as a main component, and is preferably a layer formed on the base layer 23.

  Examples of the method for forming the electrode layer 12 include a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. And a method using the dry process. Among these, the vapor deposition method is preferably applied.

  In addition, the electrode layer 12 is formed on the base layer 23 so that it has sufficient conductivity even without high-temperature annealing after the electrode layer 12 is formed. In addition, high temperature annealing treatment or the like after film formation may be performed.

  Examples of the alloy mainly composed of silver (Ag) constituting the electrode layer 12 include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium (AgIn). ) And the like.

  Further, it is also preferable to add about 2 atomic% of aluminum (Al) or gold (Au) to silver and co-evaporate.

  The electrode layer 12 as described above may have a configuration in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  Furthermore, the electrode layer 12 preferably has a layer thickness in the range of 5 to 30 nm. When the layer thickness is less than 30 nm, the light absorption component or reflection component of the layer is small, and the transmittance of the first transparent electrode 12 is increased. Moreover, when the layer thickness is thicker than 5 nm, the conductivity of the layer can be sufficiently secured. Preferably it is the range of 8-20 nm, More preferably, it is the range of 10-15 nm.

(4.3) Effect of first electrode and second electrode The first electrode 25 having the above-described configuration is configured by using, for example, an organic compound having at least one atom selected from a nitrogen atom and a sulfur atom. The electrode layer 12 made of silver or an alloy containing silver as a main component is provided on the underlying layer 23. Thereby, when the electrode layer 12 is formed on the base layer 23, the silver atoms constituting the electrode layer 12 interact with the compound containing nitrogen atoms or sulfur atoms constituting the base layer 23, and silver The diffusion distance of atoms on the surface of the underlayer 23 is reduced, and aggregation of silver is suppressed.

  Here, in general, in the film formation of the electrode layer 12 mainly composed of silver, since a thin film is grown by a nuclear growth type (Volume-Weber: VW type), the silver particles are easily isolated in an island shape, and the layer thickness is increased. When the thickness is thin, it is difficult to obtain conductivity, and the sheet resistance value becomes high. Therefore, in order to ensure conductivity, it is necessary to increase the layer thickness. However, if the layer thickness is increased, the light transmittance is lowered, so that it is not suitable as the first electrode.

  However, according to the first electrode 25 of the present invention, since aggregation of silver is suppressed on the underlayer 23 as described above, in forming the electrode layer 12 made of silver or an alloy containing silver as a main component. Then, a single layer growth type (Frank-van der Merwe: FM type) thin film is grown.

  Therefore, as described above, the electrode layer 12 made of silver or an alloy containing silver as a main component has a thinner layer and the conductivity is ensured, so that the first electrode 25 and the second electrode 46 It becomes possible to achieve both improvement in conductivity and improvement in light transmission.

  Furthermore, since the first electrode and the second electrode according to the present invention can be adjusted to be thin in a range in which specular reflection at the silver electrode does not occur, it is possible to contribute to an improvement in light emission luminance. In particular, by making the second electrode a transparent electrode layer made of silver or an alloy containing silver as a main component, the scattered light or reflected light from the organic light emitting layer is emitted by a black material disposed behind the second electrode. Since it can absorb, contrast ratio can be raised more.

(5) Organic light emitting layer (5.1) Light emitting layer The organic light emitting layer 45 includes at least a light emitting layer 45c.

  The light emitting layer 45c used in the present invention preferably contains a phosphorescent light emitting compound as a light emitting material. Note that a fluorescent material may be used as the light emitting material, or a phosphorescent light emitting compound and a fluorescent material may be used in combination.

  The light emitting layer 45c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 45d and holes injected from the hole transport layer 45b, and the light emitting portion is the light emitting layer 45c. Even within the layer, it may be the interface between the light emitting layer 45c and the adjacent layer.

  The light emitting layer 45c is not particularly limited in its configuration as long as the contained light emitting material satisfies the light emission requirements. There may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer (not shown) between the light emitting layers 45c.

  The total thickness of the light emitting layer 45c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained.

  The total thickness of the light emitting layer 45c is a layer thickness including the intermediate layer when a non-light emitting intermediate layer exists between the light emitting layers 45c.

  In the case of the light emitting layer 45c having a configuration in which a plurality of layers are stacked, the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably adjusted within a range of 1 to 20 nm. preferable. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer 45c as described above is formed by forming a known light emitting material or host compound by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. be able to.

  A light-emitting dopant (also referred to as a light-emitting dopant compound) and a host compound contained in the light-emitting layer will be described.

(5.1.1) Host Compound Here, in the present invention, the host compound is a compound contained in the light emitting layer, the mass ratio in the layer is 20% or more, and room temperature (25 ° C.). Is defined as a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.1. The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. 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. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  The light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). Light emitting host).

  As the known host compound that may be used in combination, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable.

  Specific examples of known host compounds include, but are not limited to, compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  The light emitting dopant used in the present invention will be described.

  From the viewpoint of obtaining an organic EL device with higher luminous efficiency, the light emitting layer of the organic EL device of the present invention preferably contains a phosphorescent dopant simultaneously with the host compound.

(5.1.2) Phosphorescent dopant The phosphorescent dopant used in the present invention is a compound in which light emission from an excited triplet is observed, and specifically, phosphorescent light is emitted at room temperature (25 ° C.). Although it is a compound and a phosphorescence quantum yield is defined as a compound 0.01 or more at 25 degreeC, a preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

  There are two types of light emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. The energy transfer type that obtains light emission from the phosphorescent dopant, and the other is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. Although it is a trap type, in any case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.

  Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.

Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 /. No. 0202194, U.S. Patent Application Publication No. 2007/0087321, U.S. Patent Application Publication No. 2005/0244673, Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. US Patent Application Publication No. 2009/0108737, US Patent Application Publication No. 2009/0039776, US Patent No. 6921915, US Patent No. 6,687,266, US Patent Application Publication No. 2007/0190359. Specification, US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Patent No. 7250226, US Patent No. 7396598 Writing, U.S. Patent Application Publication No. 2006/0263635, U.S. Patent Application Publication No. 2003/0138657, U.S. Patent Application Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308
(2007), Organometallics 23, 3745 (2004), Appl. Phys. Lett. 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599. Description, US Pat. No. 7,534,505, US Pat. No. 7,445,855, US Patent Application Publication No. 2007/0190359, US Patent Application Publication No. 2008/0297033, US Pat. No. 7,338,722 ,USA Published Patent Application No. 2002/0134984, U.S. Pat. No. 7,279,704, U.S. Patent Application Publication No. 2006/098120, U.S. Patent Application Publication No. 2006/103874, International Publication No. 2005/076380. International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, International Publication No. 2011/157339, International Publication No. 2010/086089, International Publication No. Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, US Patent Application Publication No. 2012/228583 ,USA Japanese Patent Application Publication No. 2012/212126, Japanese Patent Application Laid-Open No. 2012-069737, Japanese Patent Application Laid-Open No. 2011-181303, Japanese Patent Application Laid-Open No. 2009-114086, Japanese Patent Application Laid-Open No. 2003-81988, Japanese Patent Application Laid-Open No. 2002-302671. Japanese Patent Laid-Open No. 2002-363552.

  Among these, a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.

  In the organic EL element 50, at least one light emitting layer 45c may contain two or more types of phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer 45c is the thickness of the light emitting layer 45c. It may change in the direction.

  The phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 45c.

  In addition, a fluorescent material can be used for the light emitting layer 45c. Examples of the fluorescent material include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes. Fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

(5.2) Injection layer (hole injection layer, electron injection layer)
The injection layer is a layer provided between the electrode and the light emitting layer 45c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its forefront of industrialization (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of the 2nd volume of “S. Co., Ltd.”, which includes a hole injection layer 45a and an electron injection layer 45e.

  The injection layer can be provided as necessary. The hole injection layer 45a may exist between the anode and the light emitting layer 45c or the hole transport layer 45b, and the electron injection layer 45e may exist between the cathode and the light emitting layer 45c or the electron transport layer 45d.

  The details of the hole injection layer 45a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the electron injection layer 45e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically, strontium, aluminum and the like are represented. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 45e of the present invention is desirably a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 μm although it depends on the material.

(5.3) Hole transport layer The hole transport layer 45b is made of a hole transport material having a function of transporting holes. In a broad sense, the hole injection layer 45a and the electron blocking layer are also formed into the hole transport layer 45b. included. The hole transport layer 45b 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.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially 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 and also two fused aromatic rings described in US Pat. No. 5,061,569 In the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-30868 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in Japanese Patent Publication are linked in a starburst type ) 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.

  JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer 45b is 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 inkjet method, or an LB method. be able to. Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 45b, Usually, 5 nm-about 5 micrometers, Preferably it is the range of 5-200 nm. The hole transport layer 45b may have a single layer structure composed of one or more of the above materials.

  Alternatively, the material of the hole transport layer 45b can be doped with impurities to increase the p property. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer 45b because an element with lower power consumption can be manufactured.

(5.4) Electron Transport Layer The electron transport layer 45d is made of a material having a function of transporting electrons. In a broad sense, the electron transport layer 45e and a hole blocking layer (not shown) are also included in the electron transport layer 45d. The electron transport layer 45d can be provided as a single layer structure or a stacked structure of a plurality of layers.

  In the electron transport layer 45d having a single layer structure and the electron transport layer 45d having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 45c was injected from the cathode. What is necessary is just to have the function to transmit an electron to the light emitting layer 45c. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Further, 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 are also used as the material for the electron transport layer 45d. Can do. 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 ₃ ), 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), etc., and the central metals of these metal complexes are In, Mg Metal complexes replaced by Cu, Ca, Sn, Ga, or Pb can also be used as the material for the electron transport layer 45d.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with alkyl groups or sulfonic acid groups can be preferably used as the material for the electron transport layer 45d. Further, a distyrylpyrazine derivative exemplified also as a material of the light emitting layer 45c can be used as a material of the electron transport layer 45d, and similarly to the hole injection layer 45a and the hole transport layer 45b, n-type -Si, n An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 45d.

  The electron transport layer 45d can be formed by thinning the above 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 layer thickness of 45 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it is the range of 5-200 nm. The electron transport layer 45d may have a single-layer structure made of one or more of the above materials.

  In addition, the electron transport layer 45d can be doped with impurities to increase the n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, the electron transport layer 45d preferably contains potassium, a potassium compound, or the like. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 45d is increased, a device with lower power consumption can be manufactured.

  Further, as the material (electron transporting compound) of the electron transport layer 45d, the same material as that of the base layer 23 described above may be used. The same applies to the electron transport layer 45d that also serves as the electron injection layer 45e, and the same material as that of the base layer 23 described above may be used.

(5.5) Blocking layer (hole blocking layer, electron blocking layer)
The blocking layer may be further provided as the organic light emitting layer 45 in addition to the above functional layers. 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.

  In a broad sense, the hole blocking layer has the function of the electron transport layer 45d. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer 45d mentioned later can be used as a hole-blocking layer based on this invention as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 45c.

  On the other hand, the electron blocking layer has the function of the hole transport layer 45b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. be able to. Moreover, the structure of the positive hole transport layer 45b can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer according to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

Film formation of each of the hole injection layer 45a, the hole transport layer 45b, the light emitting layer 45c, the electron transport layer 45d, and the electron injection layer 45e described above is performed by spin coating, casting, ink jet, vapor deposition, and printing. However, the vacuum deposition method or the spin coating method is particularly preferable from the viewpoints that a homogeneous film is easily obtained and pinholes are hardly generated. Further, different film formation methods may be applied for each layer. When a vapor deposition method is employed for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is 1 × 10 ⁻⁶ to 1 × 10. It is desirable to select each condition as appropriate within a range of ⁻² Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a layer thickness of 0.1 to 5 μm.

(6) Extraction electrode (not shown)
The extraction electrode is for electrically connecting the first electrode 25 and the second electrode 46 and an external power source, and the material thereof is not particularly limited and a known material can be preferably used. A metal film such as a MAM electrode (Mo / Al · Nd alloy / Mo) having a three-layer structure can be used.

(7) Auxiliary electrode (not shown)
The auxiliary electrode is provided for the purpose of reducing the resistance of the first electrode 25 and the second electrode 46, and is provided in contact with the electrode layer 12 of the first electrode 25 and the electrode layer of the second electrode 46. The material for forming the auxiliary electrode is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed in a range not affected by extraction of the emitted light h from the light extraction surface.

  Examples of a method for forming such an auxiliary electrode include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method. The line width of the auxiliary electrode is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode is preferably 1 μm or more from the viewpoint of conductivity.

(8) Electrode protective layer (not shown)
In the present invention, an electrode protective layer (not shown) containing an organic or inorganic compound is formed between the second electrode 46 and the sealing member 48 to smooth the surface of the second electrode. Moreover, it is preferable because of sufficient mechanical protection. In addition, by containing an organic or inorganic compound, when the sealing member 48 is laminated, the sealing strength is high because the sealing member 48 is solid-sealed.

  The electrode protective layer as described above preferably has flexibility, and a thin polymer film or a thin metal film can be used. The organic compound used in the base layer or the organic light emitting layer is appropriately used. It is also preferable that the layer is selected and formed by the coating method or the vapor deposition method.

  The electrode protective layer used in the present invention preferably contains a metal oxide from the viewpoint of solid sealing, and specific examples of the metal oxide include molybdenum oxide.

  The preferred thickness of the electrode protective layer used in the present invention can be appropriately set according to the purpose, but is preferably about 10 nm to 10 μm, more preferably about 15 nm to 1 μm, and more preferably 20 to 20 μm. More preferably, it is in the range of 500 nm.

(9) Sealing member The sealing member 48 covers the organic EL element 50, and the plate-like (film-like) sealing member 48 is fixed to the resin base material 26 side by the resin layer 47. The sealing member 48 is provided in a state of covering at least the organic light emitting layer 45, and is provided in a state of exposing the terminal portions (not shown) of the translucent electrode 25 and the counter electrode 46. Further, an electrode may be provided on the sealing member 48 so that the terminal portions of the first electrode 25 and the second electrode 46 of the organic EL element 50 are electrically connected to this electrode.

  Specific examples of the plate-like (film-like) sealing member 48 include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thin film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  Especially, since the element can be thinned, a polymer substrate in the form of a thin film can be preferably used as the sealing member 48. In that case, as described above, the sealing member 48 itself may be a resin base material containing a black material. For example, a commercially available ND filter can be used as it is as a sealing member.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) as measured by a method according to JIS-K-7126-1987 as a gas barrier property. Hereinafter, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS-K-7129-1992 is 1 × 10 ⁻³ g / (m ² · 24h) or less.

  In order to satisfy the gas barrier property, the gas barrier layer described in the section (3) Resin base material can be suitably used.

  Further, the above substrate material may be processed into a concave plate shape and used as the sealing member 48. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  Moreover, not only this but a metal material may be used. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. By using such a metal material as a sealing member 48 in the form of a thin film, the entire light-emitting panel provided with the organic EL element can be thinned.

(10) Resin Layer The resin layer 47 for fixing the sealing member 48 to the resin base material 26 side seals the organic EL element 50 sandwiched between the sealing member 48 and the resin base material 26. Used as a sealing agent. The resin layer 47 is applied on the bonding surface of the sealing member 48 or the resin base material 26 in such a manner that an uncured resin material is dispersed and applied to a plurality of locations, and the sealing member 48 and the resin base are interposed through these resin materials. After the materials 26 are pressed against each other, the resin material is cured.

  Here, the resin material is applied in a bead shape at predetermined intervals, and an air escape passage is formed between the beads. Thereby, mixing of bubbles into the resin layer 47 after bonding can be prevented by applying a relatively simple resin material. Note that “bead” means a resin material applied in a continuous linear shape, and in the following description, a resin material applied in a linear shape is referred to as “bead”.

  The bead made of a resin material is preferably formed in a dome shape that is substantially point-contacted at the time of initial contact with the other bonding surface in a cross-sectional view substantially orthogonal to the extending direction. With this shape, the contact area between the resin material and the bonding surface can be reduced at the initial contact immediately after the resin material contacts the bonding surface, and air can be hardly mixed into the resin layer 47. . Then, while pressing the outer surface of at least one member of the sealing member 48 and the resin base material 26 arranged to face each other through the resin material, the pressing pressure portion is moved in the extending direction of the bead. The passage air between the beads can be surely expelled to the outside.

  As such a resin layer 47, it is preferable to use a photocurable resin. For example, photo-radically polymerizable resins mainly composed of various (meth) acrylates such as polyester (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyurethane (meth) acrylate, epoxy, vinyl ether, etc. Photocationic polymerizable resins mainly composed of the above resins, thiol / ene addition type resins, and the like. Among these photo-curing resins, an epoxy resin-based photo-cationic polymerizable resin having a low shrinkage of the cured product, a small outgas, and excellent long-term reliability is preferable.

  Moreover, as such a resin layer 47, heat | fever and chemical curing type (two-component mixing) resin, such as an epoxy type, can be used. Hot melt polyamide, polyester, and polyolefin can also be used. Moreover, a cationic curing type ultraviolet curing epoxy resin can be used.

  In addition, the organic material which comprises the organic EL element 50 may deteriorate with heat processing. For this reason, it is preferable to use a resin material that can be adhesively cured from room temperature to 80 ° C.

[Method for producing organic EL element]
Here, as an example, a method for manufacturing the organic EL element 50 shown in FIG. 1 will be described.

  First, the gas barrier layer 27 is formed on the resin base material 26 by an appropriate method such as the above-described CVD method or vapor deposition method so as to have a layer thickness of 1 μm or less, preferably 10 to 100 nm. Next, the polysilazane modified layer 11 according to the present invention is preferably formed by a coating method and then subjected to a modification treatment by irradiation with vacuum ultraviolet rays, and an underlayer 23 containing an organic compound containing nitrogen atoms or sulfur atoms is formed thereon. Vapor deposition method is performed by vapor deposition or the like, and then the electrode layer 12 mainly composed of silver (or an alloy containing silver) has a layer thickness within a range of 5 to 30 nm, preferably within a range of 8 to 20 nm. The first electrode 25 to be an anode is formed by an appropriate method such as the above.

Next, a hole injection layer 45 a, a hole transport layer 45 b, a light emitting layer 45 c, an electron transport layer 45 d, and an electron injection layer 45 e are formed in this order to form an organic light emitting layer 45. The film formation of each of these layers includes spin coating, casting, ink jet, vapor deposition, and printing, but vacuum vapor deposition is easy because a homogeneous film is easily obtained and pinholes are difficult to generate. The method or spin coating method is particularly preferred. Further, different film formation methods may be applied for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 × 10 ⁻⁶ to 1 × 10 ^−2. It is desirable to appropriately select each condition within the ranges of Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of −50 to 300 ° C., and layer thickness of 0.1 to 5 μm.

  After forming the organic light emitting layer 45 as described above, a second electrode 46 serving as a cathode is formed thereon by an appropriate film forming method such as a vapor deposition method or a sputtering method. At this time, the second electrode 46 is formed in a pattern in which a terminal portion is drawn from the upper side of the organic light emitting layer 45 to the periphery of the resin base material 26 while being insulated from the first electrode 25 by the organic light emitting layer 45. To do.

  Next, a black material is disposed on the opposite side of the second electrode 46 from the organic light emitting layer 45. The arrangement of the black material is as described above.

  Thereby, the organic EL element 50 is obtained. Thereafter, a sealing member 48 that covers at least the organic light emitting layer 45 is provided in a state where the terminal portions of the first electrode 25 and the second electrode 46 in the organic EL element 50 are exposed.

  As described above, a desired organic EL element is obtained on the resin base material 26. In the production of such an organic EL element 50, it is preferable to produce the organic light emitting layer 45 to the second electrode 46 consistently by a single vacuum, but the resin base material 26 is taken out from the vacuum atmosphere in the middle. Different film forming methods may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  When a DC voltage is applied to the organic EL element 50 thus obtained, the first electrode 25 as an anode has a positive polarity, the second electrode 46 as a cathode has a negative polarity, and a voltage of 2 to 2 is applied. Luminescence can be observed when about 40 V is applied. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

[Use of organic EL elements]
The organic EL element of the present invention is a surface light emitter and can be used as various light sources. For example, lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, It can be used as a light source for an optical sensor.

  In particular, the organic EL element of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a type that directly recognizes a still image or a moving image. It may be used as a display device (display). In particular, the organic EL device of the present invention has a high contrast ratio because a black material is disposed therein, and when used in a small display device such as a smartphone or a tablet, the contrast is high and an excellent display performance can be realized. it can.

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. In addition, a color or full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
[Production of bottom emission type organic EL element]
[Production of Organic EL Element of Sample 101]
Using a 125 μm thick polyester film (Teijin DuPont Films Co., Ltd., extremely low heat yield PET Q83) as a resin base material, a gas barrier layer is formed on the resin base material by a sputtering method using a commercially available sputtering apparatus. A SiO ₂ film having a thickness of 100 nm was formed.

A 150 nm-thick ITO (Indium Tin Oxide) film is formed by sputtering using a commercially available sputtering device on the surface opposite to the surface on which the SiO ₂ film of the resin substrate is formed. Then, patterning was performed by a photolithography method to form a first electrode. The pattern was such that the light emission area was 50 mm square.

Subsequently, the pressure was reduced to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A transport layer (HTL) was provided.

  Next, compound A-3 (blue light emitting dopant), compound A-1 (green light emitting dopant), compound A-2 (red light emitting dopant) and compound H-1 (host compound), compound A-3 having a film thickness In contrast, the vapor deposition rate was changed depending on the location so that it was linearly 35% by mass to 5% by mass, and the compound A-1 and the compound A-2 each had a concentration of 0.2% by mass without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / sec, the compound H-1 was co-deposited to a thickness of 70 nm by changing the deposition rate depending on the location from 64.6% to 94.6% by mass. A light emitting layer was formed.

  Thereafter, Compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm.

  In addition, the said compound HT-1, compound A-1 to 3, compound H-1, and compound ET-1 are the compounds shown below.

更に、市販の真空蒸着装置の基材ホルダーに固定し、窒素原子を含む例示化合物Ｎｏ．１０をタンタル製抵抗加熱ボートに入れ、これら基材ホルダーと加熱ボートとを真空蒸着装置の第１真空槽内に取り付けた。また、タングステン製の抵抗加熱ボートに銀（Ａｇ）を入れ、真空蒸着装置の第２真空槽内に取り付けた。

Furthermore, it is fixed to a base material holder of a commercially available vacuum deposition apparatus, and exemplified compound No. 1 containing nitrogen atoms. 10 was put in a resistance heating boat made of tantalum, and the base material holder and the heating boat were mounted in the first vacuum chamber of the vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after depressurizing the first vacuum tank to 4 × 10 ⁻⁴ Pa, the exemplified compound No. A heating boat containing 10 is energized and heated, and a base layer containing a compound containing nitrogen atoms is provided on the electron transport layer at a deposition rate of 0.1 nm / second to 0.2 nm / second with a thickness of 10 nm. It was. Next, the base material formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. As a result, an electrode layer made of silver having a thickness of 9 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second, a mask pattern was formed so that the light emitting area was 50 mm square, and the second electrode was formed. Formed.

As a sealing member, a ND filter (ND = 4.0) manufactured by Fuji Film, on which a gas barrier layer of a SiO ₂ film having a thickness of 100 nm is formed by sputtering, and an epoxy thermosetting type as an adhesive is used. Using an adhesive (Elephant CS manufactured by Yodogawa Paper Co., Ltd.), suction 20 at a reduced pressure (1 × 10 ⁻³ MPa or less) under a load of 0.04 MPa at 80 ° C. in a glove box having an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less. The organic EL element of Sample 101 was produced by solid-sealing with a vacuum press so that the gas barrier layer of the ND filter was on the element side toward the organic EL element under the conditions of seconds and press for 20 seconds. The ND filter is a light absorption layer containing the black material according to the present invention.
[Production of organic EL element of sample 102]
In the production of the organic EL element of Sample 101, the same procedure was performed except that the first electrode, the organic light emitting layer, and the second electrode were formed on the SiO ₂ film that was the gas barrier layer on the resin substrate. An organic EL element was produced.
[Production of Organic EL Element of Sample 103]
In the preparation of the organic EL element of Sample 102, the gas barrier layer of the SiO ₂ film was changed to a gas barrier layer by a CVD method prepared by the following procedure, and a polysilazane-containing coating solution was applied on the gas barrier layer by the following procedure. An organic EL element of Sample 103 was produced in the same manner except that a polysilazane modified layer was formed, and a first electrode, an organic light emitting layer, and a second electrode were formed and sealed thereon (polysilazane modified layer was (Indicated in the table as PHPS layer.)

(Formation of gas barrier layer)
The base material was mounted on the gas barrier layer manufacturing apparatus shown in FIG. 5, and the gas barrier layer was formed to a thickness of 300 nm on the base material under the following film forming conditions (plasma CVD conditions).

Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 1.2 kW
Frequency of power source for plasma generation: 80 kHz
Film transport speed: 0.5 m / min
(Preparation of polysilazane-containing coating solution)
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-) Perhydropolysilazane 20% by weight dibutyl ether solution (AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) containing 5% by weight of 1,6-diaminohexane (TMDAH) In a solvent mixed so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, the coating solution is mixed so that the solid content of the coating solution is 5% by mass. Was diluted and prepared.

The coating solution obtained above was formed into a film with a thickness of 300 nm on the gas barrier layer with a spin coater, allowed to stand for 2 minutes, and then subjected to heat treatment for 1 minute on a hot plate at 80 ° C. A polysilazane modified layer not subjected to the modification treatment by lamp irradiation was formed.
[Production of Organic EL Element of Sample 104]
In the production of the organic EL element of Sample 103, after forming a polysilazane-containing layer using a polysilazane-containing coating solution, it was installed in the following vacuum ultraviolet irradiation apparatus, and the modification treatment by excimer lamp irradiation was performed in the same manner. An organic EL element of Sample 104 was produced.

Ultraviolet irradiation device: excimer irradiation device MODEL manufactured by MCOM Co., Ltd .: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
The base material on which the polysilazane layer fixed on the operating stage was formed was modified under the following conditions to form a polysilazane modified layer.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds The polysilazane modified layer is formed by a method of confirming the cross section of the layer using a transmission electron microscope (TEM), and the surface portion of the layer on the side in contact with the first electrode is exposed to vacuum ultraviolet light. It was confirmed that the layer was a two-layer structure that was a modified part and the inside of the layer was an unmodified part.
[Production of Organic EL Element of Sample 105]
In the production of the organic EL element of the sample 104, instead of the ITO electrode of the first electrode, the base layer and the electrode layer made of silver were formed on the polysilazane modified layer in the same manner as the second electrode, An organic EL element of Sample 105 was produced in the same manner except that the first electrode was used.

<< Evaluation of organic EL elements >>
(Luminescence efficiency)
Using a spectral radiance meter CS-1000 (manufactured by Konica Minolta), the front luminance and luminance angle dependency of the organic EL elements of Samples 101 to 105 were measured, and the power efficiency at the front luminance of 1000 cd / m ² was evaluated. Note that the evaluation of light emission luminance was made by comparing and comparing the relative efficiency with the power efficiency of the sample 101 as 100, and classifying and evaluating in the following five stages. The larger the value, the better the power efficiency.

5: 120 or more 4: 101-119
3: 81-100
2: 71-80
1:70 or less (leak characteristics)
The solid-sealed organic EL element was measured at room temperature three times for a forward voltage flowing at 500 μA / cm ² and its reverse voltage, and the rectification ratio was calculated from the average value. The higher the rectification ratio, the better the leak characteristics. The evaluation results (five-level evaluation) are shown in Table 3. A higher rectification ratio indicates better leakage characteristics.
Rectification ratio rank 5: Rectification ratio 10000 or more (level that drives very stably)
4: Rectification ratio of 1000 or more and less than 10,000 (level of stable driving)
3: Rectification ratio of 500 or more and less than 1,000
2: Rectification ratio of 100 or more and less than 500 (inferior level with practical problems)
1: Rectification ratio of less than 100 (very inferior, practically problematic level)
(Storability)
The organic EL elements of Samples 101 to 105 were energized in an environment of 60 ° C. and 90% RH, and the change in light emission unevenness such as the occurrence of dark spots was observed from the 0th to the 120th. The observed light emission unevenness of each sample was classified into the following five stages and evaluated. The smaller the number of occurrences, the better the heat resistant storage stability.

  On day 5: 0, dark spots and luminance unevenness were not observed, and after 120 days, the non-light emitting area was 0.1% or less of the total light emitting area, and all the generated dark spots were not easily observable visually ( 0.1 mm or less).

  4: All dark spots generated on the 0th day have a size (0.1 mm or less) that cannot be easily observed by visual observation, luminance unevenness is not observed, and the non-light emitting area is 0% of the total light emitting area after 120 days. At 2% or less, the generated dark spot maintained a size (0.1 mm or less) that cannot be easily observed visually.

  The dark spots that occurred on the 3rd day were all in a size (0.1 mm or less) that could not be easily observed visually, and after 120 days, the non-light emitting area exceeded 2% of the total light emitting area.

  2: Dark spots and luminance unevenness that can be visually discerned were observed on the 0th day, and after 120 days, the non-light emitting area exceeded 2% of the total light emitting area.

  Dark spots that can be visually discerned on day 1 and non-luminous areas with uneven brightness were observed exceeding 1% of the total light-emitting area, and non-light-emitting areas exceeded 10% of the total light-emitting area within 120 days .

  The above evaluation results (five-step evaluation) are shown in Table 3.

本発明の有機ＥＬ素子である試料１０３〜１０５は、光吸収層を具備していることによって、発光状態での目視観察により、コントラストが高く観察された。また、表３の評価結果から、比較試料１０１及び１０２に対して、発光効率、リーク特性、保存性に優れていることがわかる。特に、真空紫外光によってポリシラザン改質層を形成した試料１０４及び１０５は上記特性がさらに優れており、中でも第一電極及び第二電極に銀電極を採用した試料１０５は、特に優れた特性を実現できた。

Samples 103 to 105, which are the organic EL elements of the present invention, were observed to have a high contrast by visual observation in a light emitting state because they were provided with a light absorption layer. In addition, it can be seen from the evaluation results in Table 3 that the comparative samples 101 and 102 are excellent in luminous efficiency, leak characteristics, and storage stability. In particular, the samples 104 and 105 in which the polysilazane modified layer is formed by vacuum ultraviolet light are further excellent in the above characteristics, and the sample 105 in which the silver electrode is used for the first electrode and the second electrode among them realizes particularly excellent characteristics. did it.

Example 2
In the preparation of the sample 105 of Example 1, a carbon black-containing photoresist material was applied by spin coating on the surface of the second electrode opposite to the organic light emitting layer, and baked. A thin film having a thickness of 2 μm containing was formed. Furthermore, it replaced with the said ND filter used for the sealing member, and produced the organic EL element 201 similarly except having used the following sealing member.

(Preparation of sealing member)
As a sealing member, a polyester film with a thickness of 125 μm (manufactured by Teijin DuPont Films Co., Ltd., extremely low heat yield PET Q83) is used, and as a gas barrier layer, a commercially available sputtering apparatus is used. A SiO ₂ film was formed.

  When the same evaluation as in Example 1 was performed using the prepared sample 201, the result of the sample 105 in Example 1 was reproduced, the contrast was observed high, and excellent luminous efficiency, leakage characteristics, and storage stability were obtained. It turned out that the organic EL element which has is obtained.

  The organic electroluminescent element of the present invention is an organic light-emitting element having flexibility and excellent contrast ratio and excellent heat-resistant storage stability, and is suitably used for a flexible display device and lighting device.

DESCRIPTION OF SYMBOLS 11 Polysilazane modified layer 12 Electrode layer 23 Underlayer 25 First electrode 26 Resin base material 26a Light extraction surface 27 Gas barrier layer 30 Manufacturing apparatus 31 Delivery roll 32, 33, 34, 35 Conveyance roller 36, 37 Film formation roller 38 Gas Supply tube 39 Power source for plasma generation 40 Film 41 Magnetic field generator 43 Winding roll 45 Organic light emitting layer 45a Hole injection layer 45b Hole transport layer 45c Light emission layer 45d Electron transport layer 45e Electron injection layer 46 Second electrode 47 Resin layer 48 Sealing member 50 Organic EL optical device

Claims (4)

  An organic electroluminescence device comprising at least a first electrode, an organic light emitting layer, and a second electrode in this order on a resin base material, both of the first electrode and the second electrode being transparent electrodes, A polysilazane modified layer is provided between one electrode and the resin base material, and a light absorption layer containing a black material is provided on the opposite side of the organic light emitting layer of the second electrode. Organic electroluminescence device.   2. The organic electroluminescence device according to claim 1, wherein the polysilazane modified layer contains at least one compound selected from polysilazane and a polysilazane modified product.   The at least one of said 1st electrode and said 2nd electrode is an electrode layer with a thickness of 30 nm or less formed using silver or an alloy containing silver as a main component. 2. The organic electroluminescence device according to 2.   It is a manufacturing method of the organic electroluminescent element as described in any one of Claim 1- Claim 3, Comprising: The said polysilazane modified layer is modified by irradiating a vacuum ultraviolet light to a polysilazane content layer, and forming A method for producing an organic electroluminescence element, comprising:

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