JP6409771B2 - Organic electroluminescence device and method for manufacturing the same - Google Patents

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 that is highly flexible and can change the color of a non-light emitting region and a non-light emitting region to various colors, and a method for manufacturing the same.

  In recent years, as a planar light source body, a light emitting diode (LED) and an organic light emitting diode (OLED) using a light guide plate (film), hereinafter referred to as “organic electroluminescent element” or “organic EL”. It is also called “element”.) About LED using a light-guide plate (henceforth "light-guide plate LED"), not only general illumination but a liquid crystal display (Liquid Crystal Display: LCD) backlight etc. are used in various scenes and applications. It has come to be used (for example, refer patent document 1).

  Moreover, for example, the light guide plate LED is also incorporated in smart devices represented by smartphones and tablets whose production volume has been increasing since around 2008. In this smart device, the light guide plate LED is often incorporated as a backlight of a main display (for example, LCD) or a backlight of a common function key button outside the main display.

Here, the common function key buttons are mainly displayed with a “Home” button displayed with a mark such as a rectangle, a “Back” button displayed with an arrow mark, and a magnifying glass mark on a general smart device. This is a button having a fixed function and shape such as a “Search” button. Usually, the “Home” button, “Back” button, and “Search” button are often arranged outside the main display as common function key buttons.
The common function key button generally has a configuration in which a cover glass on which a dot-shaped diffusion member is arranged is laminated on a light guide plate LED. The dot-like diffusing member is arranged in the shape of a mark to be displayed. Accordingly, when the LED emits light, the light is guided through the light guide plate, and the light is extracted from the light extraction surface through the dot-shaped diffusion member disposed on the cover glass, so that a mark to be displayed is displayed.

However, as described above, when an LED and an OLED (organic EL element) are used as the backlight of the smart device, a part of light (hereinafter also referred to as “external incident light”) incident on the organic EL element from the outside is a cathode. The phenomenon that the light is reflected by the metal layer and emitted from the light extraction surface occurs. When the reflected external incident light is emitted from the light extraction surface, the color purity of the organic EL element when not emitting light and the non-emitting area is deteriorated, and the appearance is deteriorated. In order to prevent this problem from occurring, a polarizing plate or the like may be provided on the light extraction surface side of the organic EL element.
However, when a polarizing plate or the like is provided, there is a problem that the light transmittance itself is poor and the light emission efficiency is lowered. To solve this problem, Patent Document 2 discloses a technique for sealing a can by providing an organic coating film on a sealing member instead of providing a polarizing plate.
However, there is a problem that the flexibility of the organic EL may be impaired when the can is sealed.

U.S. Pat. No. 8,330,724 JP 2002-319485 A

  The present invention has been made in view of the above-described problems and situations, and the problem to be solved is an organic electroluminescence element that is highly flexible and can change the color of the non-light-emitting region and the non-light-emitting region to various colors. The manufacturing method is provided.

In order to solve the above-mentioned problems, the present inventor is flexible by laminating and sealing the laminate with a sealing member colored at least partially in the process of examining the cause of the above-mentioned problem. It has been found that an organic electroluminescence device having a high color and various colors in a non-light-emitting region and a non-light-emitting region can be provided.
That is, the said subject which concerns on this invention is solved by the following means.

1. An organic electroluminescence element having a laminate and a sealing member in which at least a transparent substrate, a first transparent electrode, an organic layer, and a second transparent electrode are laminated in this order,
Extract light only from the transparent substrate side,
The sealing member has a capping group member having an adhesive layer, and a layer which is colored disposed only on the adhesive layer side even without low,
The laminated body is sealed by the sealing member by laminating the sealing substrate on the surface on the second transparent electrode side through the adhesive layer. Luminescence element.

  2. 2. The organic electroluminescence element according to item 1, wherein the first transparent electrode and the second transparent electrode are metal thin films.

  3. 3. The organic electroluminescent element according to claim 1 or 2, wherein the sealing base material includes an aluminum foil subjected to an alumite treatment as a constituent element.

4). The adhesive layer, and an organic material of the insulating as adhesives, coloring an organic electroluminescent device according to any one of the first term to the third term, characterized in that it contains a.

5. The organic electroluminescent element according to item 4, wherein the content of the colorant is in the range of 0.5 to 20% by mass in the adhesive layer.

6). At least a transparent substrate, a first transparent electrode, an organic layer and a second transparent electrode have a laminate as well as the sealing member are laminated in this order, a manufacturing method of an organic electroluminescent device is taken out only light from the transparent substrate side ,
As the organic layer, at least a hole injection layer, a hole transport layer, an organic layer forming step of forming a light emitting layer, and
A sealing step of laminating the the laminate, before Kifutome member from the surface of the second transparent electrode side,
I have a,
The sealing member has a sealing substrate having at least an adhesive layer, and a colored layer disposed only on the adhesive layer side,
In the sealing step of laminating the sealing member, the sealing substrate is laminated on the laminate through the adhesive layer . A method for producing an organic electroluminescent element, comprising:

7 . 6. The method according to claim 6 , further comprising a step of forming a light emitting pattern by irradiating at least a part of the laminated body with ultraviolet rays after laminating the sealing member on the laminated body in the sealing step. method of manufacturing an organic electroluminescent device according to.

  By the above means of the present invention, it is possible to provide an organic electroluminescence device which is highly flexible and can change the color of the non-light-emitting region and the non-light-emitting region into various colors and a method for manufacturing the same.

The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.
Conventionally, there is a problem that part of light incident on the organic EL element from the outside is reflected by a metal layer such as a cathode and emitted from the light extraction surface.
On the other hand, the present inventor can prevent reflection of light incident on the organic EL element from the outside by coloring the sealing member, and the non-light emission and non-light emission by coloring. The present inventors have found that the color of the region can be various colors and that it is not necessary to provide a polarizing plate or the like, so that the organic EL element can be thinned, and the present invention has been achieved.
The inventor has also found that the color of the organic EL element in the non-light-emitting region and in the non-light-emitting region is affected by the way in which the first transparent electrode, the second transparent electrode, and the sealing member overlap, and the first transparent electrode And it discovered that the color purity of the organic EL element of the non-light-emission area | region and a non-light-emission area | region can be improved by forming a 2nd transparent electrode solidly instead of the shape of a light emission pattern.
Thus, the present invention can adjust the color of the organic EL element in the non-light-emitting region and in the non-light-emitting region. In the present invention, the color of the light emitting region is adjusted by the organic layer.

The schematic diagram which shows an example of a structure of the organic EL element of this invention The schematic diagram which shows an example of a structure of the 1st transparent electrode which concerns on this invention The schematic diagram which shows an example of a structure of the 2nd transparent electrode which concerns on this invention Schematic diagram showing the structure of the organic EL manufactured in this example The schematic diagram which shows the other structure of the organic EL manufactured in a present Example The schematic diagram which shows the other structure of the organic EL manufactured in a present Example

The organic electroluminescence element of the present invention is an organic electroluminescence element having a laminate in which at least a transparent substrate, a first transparent electrode, an organic layer, and a second transparent electrode are laminated in this order, and a sealing member, wherein the sealing member Is at least partially colored, and has at least a sealing substrate and an adhesive layer, and the laminate has the sealing substrate on the surface on the second transparent electrode side through the adhesive layer. By being laminated, it is sealed by the sealing member. This feature is a technical feature common to the inventions according to the following embodiments .
Thereby, this invention can provide the organic electroluminescent element which has high flexibility, and can make the color of a non-light-emission and a non-light-emitting area | region into various colors, and its manufacturing method.

  As an embodiment of the present invention, it is preferable that the first transparent electrode and the second transparent electrode are metal thin films from the viewpoint of manifesting the effects of the present invention. Thereby, the color of the non-light-emitting region and the non-light-emitting region can be brought close to the color in which the sealing member is colored. Moreover, when the sealing member is colored black, reflection of external incident light by the metal layer (first transparent electrode or the like) included in the organic EL layer can be suppressed.

  Furthermore, in this invention, it is preferable that the sealing base material contains the aluminum foil by which the alumite process was performed as a component. As a result, durability under a high temperature and high humidity environment is improved, and the sealing substrate is colored black, so that reflection of external incident light by the metal layer included in the organic EL layer can be suppressed. .

  Moreover, in this invention, it is preferable that the contact bonding layer contains the coloring agent. Thereby, the effect that various colors can be given to the non-light-emitting region and the non-light-emitting region can be obtained.

  Moreover, in this invention, it is preferable that the shape of the light emission pattern of an organic electroluminescent element differs from the shape of a 1st transparent electrode and a 2nd transparent electrode. That is, the first transparent electrode and the second transparent electrode are not limited to the shape of the light emission pattern, and may be formed in various shapes. Thereby, for example, the first transparent electrode and the second transparent electrode can be formed in a shape close to the shape of the transparent substrate and solid, and as a result, the color of the organic electroluminescence element in the light emitting and non-light emitting regions can be changed. Since it can be made uniform regardless of the shape of the light emitting pattern, an effect that the appearance can be improved is obtained.

  The organic electroluminescent element manufacturing method for manufacturing the organic electroluminescent element of the present invention includes an organic layer forming step of forming at least a hole injection layer, a hole transport layer, and a light emitting layer as an organic layer, and a second transparent electrode. And a non-light-emitting region and a non-light-emitting region that are highly flexible and have a sealing step of laminating a sealing member colored at least partially on the laminate from the side surface It is possible to provide a method for producing an organic electroluminescence device capable of changing the color of the material to various colors, which is preferable.

  Moreover, in this invention, it is preferable that an organic layer formation process forms at least one layer of a positive hole injection layer, a positive hole transport layer, and a light emitting layer in the shape different from a 1st transparent electrode and a 2nd transparent electrode. That is, the first transparent electrode and the second transparent electrode are not limited to the shape of the light emission pattern, and may be formed in various shapes. Thereby, for example, the first transparent electrode and the second transparent electrode can be formed in the same shape as the shape of the transparent substrate and solidly, and as a result, the color of the organic electroluminescence element in the light emitting and non-light emitting regions can be changed. Since it can be made uniform regardless of the shape of the light emitting pattern, an effect that the appearance can be improved is obtained.

  Furthermore, in this invention, after laminating the said sealing member on the said laminated body by the said sealing process, it has the process of irradiating an ultraviolet-ray to at least one part of the said laminated body, and forming the light emission pattern. Is preferred. Accordingly, since the light emitting region emits light with respect to the non-light emitting region (background region) of black or the like, a visual effect is obtained that the formed light emission pattern appears to be raised with respect to the non-light emitting region. be able to.

  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 element of the present invention is an organic electroluminescence element having a laminate in which at least a transparent substrate, a first transparent electrode, an organic layer, and a second transparent electrode are laminated in this order, and a sealing member, wherein the sealing member Is at least partially colored, and has at least a sealing substrate and an adhesive layer, and the laminate has the sealing substrate on the surface on the second transparent electrode side through the adhesive layer. By being laminated, it is characterized by being sealed by the sealing member. With such a configuration, the flexibility is high, and the color of the non-light-emitting region and the non-light-emitting region can be various colors. An organic electroluminescence element can be provided. In the present invention, the color at the time of light emission in the light emitting region is adjusted by the organic layer.

≪Configuration of organic EL element≫
An example of the organic EL element of the present invention is shown in FIG.
As shown in FIG. 1, the organic EL element 1 is formed by laminating a sealing member 105 on a laminate in which a first transparent electrode 4, an organic layer 6, and a second transparent electrode 12 are sequentially laminated on a transparent substrate 2. Configured.

(Laminate)
The organic EL element 1 of the present invention is characterized in that it includes a laminate 13 in which at least a transparent substrate 2, a first transparent electrode 4, an organic layer 6, and a second transparent electrode 12 are laminated in this order. In the present invention, the laminated body 13 is sealed by the sealing member 105 by laminating the sealing base material 105a via the adhesive layer 105b on the surface on the second transparent electrode 12 side, as will be described later. ing.

<Organic layer>
Although the preferable specific example of the layer structure of the organic layer 6 of this invention is shown below, this invention is not limited to these.

(I) Hole injection transport layer / light emitting layer / electron injection transport layer (ii) Hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer (iii) Hole injection transport layer / electron blocking layer / Light emitting layer / hole blocking layer / electron injection transport layer (iv) Hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer (v) Hole injection layer / hole transport layer / light emitting layer / Hole blocking layer / electron transport layer / electron injection layer (vi) Hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer

  Examples of the method for forming each layer constituting the organic layer 6 include a vacuum deposition method, a spin coating method, a casting method, an LB method (Langmuir-Blodget method), an ink jet method, a spray method, a printing method, a slot type coater method, and the like. The film can be formed by a known thin film forming method.

  Hereinafter, each layer which comprises the organic EL element 1 of this invention is demonstrated.

<Light emitting layer>
The light emitting layer preferably contains a host compound and a light emitting dopant.
The light-emitting dopant contained in the light-emitting layer may be contained at a uniform concentration in the thickness direction of the light-emitting layer, or may have a concentration distribution.
The thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film to be formed, preventing the application of unnecessary high voltage during light emission, and improving the stability of the emitted color against the drive current. It is preferable to adjust within the range of 5 to 200 nm, and more preferably within the range of 10 to 100 nm.
Hereinafter, the host compound and phosphorescent dopant contained in the light emitting layer will be described.

(1) Host compound The host compound used in the present invention is not particularly limited in terms of structure, but is typically a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, or a thiophene derivative. Those having basic skeletons such as furan derivatives and oligoarylene compounds, carboline derivatives and diazacarbazole derivatives (where diazacarbazole derivatives are at least one carbon of the hydrocarbon ring constituting the carboline ring of the carboline derivative) Represents an atom substituted with a nitrogen atom.) And the like.

  A host compound may be used independently and may be used in combination of multiple types.

  The host compound used in the light emitting layer according to the present invention may be a 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 (evaporation polymerizable light emitting host). )

As the host compound, a compound having a hole transporting ability or an electron transporting ability, which prevents a long wavelength emission and has a high Tg (glass transition temperature) is preferable. In the present invention, a compound having a glass transition point of 90 ° C. or higher is preferable, and a compound having a glass transition temperature of 130 ° C. or higher is preferable because excellent characteristics can be obtained.
Here, the glass transition point (Tg) is a value determined by a method based on JIS K 7121 using DSC (Differential Scanning Colorimetry).

In the present invention, a conventionally known host compound can also be used.
As specific examples of conventionally known host compounds, compounds described in the following documents can be suitably used. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, US 2003/0175553, US 2006/0280965. US Patent Publication No. 2005/0112407, US Patent Publication No. 2009/0017330, US Patent Publication No. 2009/0030202, US Patent Publication No. 2005/238919, International Publication No. 0392 No. 4, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. 2007/063754 International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, International Publication No. 2012/023947, Special JP 2008-074939 A, JP 2007-254297 A, European Patent No. 2034538, and the like.

  When the organic EL device 1 of the present invention has a plurality of light emitting layers, the host compound may be different for each light emitting layer, but the same compound is preferable in terms of production efficiency and process management.

In addition, it is preferable that the host compound has a lowest excited triplet energy (T1) larger than 2.7 eV because higher luminous efficiency can be obtained.
The lowest excited triplet energy as used in the present invention refers to the peak energy of an emission band corresponding to the transition between the lowest vibrational bands of a phosphorescence emission spectrum observed at a liquid nitrogen temperature after dissolving a host compound in a solvent.

(2) Phosphorescence emission dopant The phosphorescence emission dopant which can be used for this invention can be selected from a well-known thing. For example, it can be selected from a complex compound containing a group 8-10 metal in the periodic table of elements, preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex. Of these, iridium compounds are most preferred.
When producing the organic EL element 1 that emits white light, a phosphorescent light emitting material is preferable as the light emitter responsible for light emission in at least the green, yellow, and red regions.

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

  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 Publication No. 2006/835469, US Patent Publication No. 2006/020202194. The compounds described in the specification, US Patent Publication No. 2007/0087321, US Patent Publication No. 2005/0244673, and the like can be mentioned.

  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 Publication No. 2002/0034656, US Pat. No. 7,332,232, US Patent Publication No. 2009/0108737, US Patent Publication No. 2009/0039776, US Patent No. 6921915, US Patent No. 6,687,266, US Patent Publication No. 2007/0190359, US Patent Publication No. 2006 No./0008670, U.S. Patent Publication No. 2009/0165846, U.S. Patent Publication No. 2008/0015355, U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598, U.S. Patent Publication No. 2006 / 026363 Pat, U.S. Patent Publication No. 2003/0138657, U.S. Patent Publication No. 2003/0152802, may be mentioned compounds described in U.S. Patent No. 7,090,928 Pat like.

  Also, 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 Publication No. 2006/0251923, US Publication No. 2005/0260441, US Pat. No. 7,393,599. U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,445,855, U.S. Patent Publication No. 2007/0190359, U.S. Patent Publication No. 2008/0297033, U.S. Pat. No. 7,338,722, U.S. Pat. No. 2002 0134984 Pat, U.S. Pat. No. 7279704, U.S. Patent Publication No. 2006/098120, compounds described in U.S. Patent Publication No. 2006/103874 Pat like can be mentioned.

  Furthermore, 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. No., International Publication No. 2010/086089, International Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, JP2012-069737, JP2009-114086, JP2003-81988, JP2002-302671, JP2002-363552, and the like.

(3) Fluorescent luminescent dopant Fluorescent luminescent dopants (also referred to as fluorescent dopants or fluorescent emitters) 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.

<Injection layer: hole injection layer, electron injection layer>
The injection layer can be provided as needed. If it is a hole injection layer, it is between the first transparent electrode 4 (anode, anode) and the light emitting layer or hole transport layer, and if it is an electron injection layer, it is the second. You may exist between the transparent electrode 12 (cathode, cathode) and a light emitting layer or an electron carrying layer.

  An injection layer is a layer provided between an electrode and a light-emitting layer in order to lower drive voltage or improve light emission luminance. “An organic EL element and its forefront of industrialization (November 30, 1998, NTS) (Published by the company) "Chapter 2 Chapter 2" Electrode Material "(pages 123-166) in detail, there are a hole injection layer and an electron injection layer.

  Details of the hole injection layer (anode buffer layer) are also described in JP-A-9-45479, 9-260062, and 8-288069. Specific examples include copper phthalocyanine. Phthalocyanine buffer layer typified by (2), oxide buffer layer typified by vanadium oxide, amorphous carbon buffer layer, and polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene. Moreover, it is also preferable to use the material described in Japanese translations of PCT publication No. 2003-519432 gazette.

  The hole injection layer may be used by mixing a plurality of materials, but in the present invention, it is preferably formed by forming a single organic compound. The reason is that, when a plurality of materials are used in combination, the risk of performance fluctuation due to fluctuation in the mixing ratio during production, for example, concentration fluctuation in the surface of the film-forming substrate is increased.

  Although there is no restriction | limiting in particular about the layer thickness of a positive hole injection layer, Usually, it exists in the range of about 0.1-100 nm, Preferably it exists in the range of 1-30 nm.

  Suitable materials for the electron injection layer include alkali metals, alkaline earth metals, and compounds thereof having a work function of 3 eV or less in the electron injection layer provided between the electron transport layer and the cathode. Specific examples of the alkali metal compound include potassium fluoride, lithium fluoride, sodium fluoride, cesium fluoride, lithium oxide, lithium quinoline complex and cesium carbonate, and lithium fluoride and cesium fluoride are preferable. .

  Although there is no restriction | limiting in particular about the layer thickness of an electron injection layer, Usually, it exists in the range of about 0.1-10 nm, Preferably it exists in the range of 0.1-2 nm.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and an extremely small ability to transport holes. By blocking holes while transporting electrons by the hole blocking layer, the recombination probability between electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer as needed.
The hole blocking layer is preferably provided adjacent to the light emitting layer.

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

  The thickness of the hole blocking layer and the electron blocking layer according to the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

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

The hole transport material has either a function of injecting or transporting holes or an electron barrier property, and may be either an organic substance or an inorganic substance. 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, conductive polymer oligomers, particularly thiophene oligomers.
As the hole transporting material, those described above can be used, but it is further preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, particularly an aromatic tertiary amine compound.

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

Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. 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-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004), JP-A-11-251067, J. MoI. Huang et. al. It is also possible to use a hole transport material that has a so-called p-type semiconducting property, as described in the literature (Applied Physics Letters 80 (2002), p. 139) and Japanese translations of PCT publication No. 2003-519432. it can. 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 may have a single layer structure composed of one or more of the above materials.

  Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer, Usually, it exists in the range of about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm.

<Electron transport layer>
The electron transport layer is made of a material having a function of transporting electrons.
The electron transport layer can be provided as a single layer or a plurality of layers.

  The electron transport material used for the electron transport layer may have any function of transmitting electrons injected through the second transparent electrode 12 (cathode) to the light emitting layer. Can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, bipyridyl derivatives, fluorenylidenemethane derivatives, carbodiimides, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. In addition, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

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

  A plurality of materials may be mixed and used for the electron transport layer. Alkali metal, alkaline earth metal, alkali metal compound or alkaline earth metal compound can be doped, but the electron transport layer according to the present invention is formed by forming a single organic compound. Is preferred. The reason is that, when a plurality of materials are used in combination, the risk of performance fluctuation due to fluctuation in the mixing ratio during production, for example, concentration fluctuation in the surface of the film-forming substrate is increased.

  The glass transition temperature of the organic compound contained in the electron transport layer is preferably 110 ° C. or higher because better high temperature storage stability and high temperature process stability can be obtained.

  Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, it exists in the range of about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm.

<Transparent substrate>
The transparent substrate 2 (also referred to as a substrate, a substrate, a substrate, or a support) applied to the organic EL element 1 of the present invention is not particularly limited in the type of glass, plastic, etc., and may be transparent. . In the organic EL element 1 of the present invention, light is extracted from the transparent substrate 2 side. Examples of the transparent substrate 2 that is preferably used include glass, quartz, and a transparent resin film. A particularly preferable transparent substrate 2 is a resin film that can give flexibility to the organic EL element 1. The “transparent substrate” in the present invention is a substrate having a light transmittance of 50% or more at a light wavelength of 550 nm, preferably. The base material is 70% or more, and more preferably 80% or more.

  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, Cycloolefins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Examples thereof include resins.

An inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film, and the water vapor permeability measured by a method according to JIS K 7129-1992 is 0.01 g / (m ² 24h) The following gas barrier film is preferable, and the oxygen permeability measured by a method based on JIS K 7126-1992 is 1 × 10 ⁻³ ml / (m ² · 24h · atm). In the following, a high gas barrier film having a water vapor permeability of 1 × 10 ⁻³ g / (m ² · 24 h) or less is preferable, and further, an oxygen permeability is 1 × 10 ⁻⁵ ml / (m ^2. It is particularly preferable that 24 h · atm) or less and the water vapor permeability is 1 × 10 ⁻⁵ / (m ² · 24 h).

  As a material for forming the gas barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of the element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the gas barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination order of the layer which consists of an inorganic layer and an organic material, It is preferable to laminate | stack both alternately several times.

  The method for forming the gas barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but those using an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 are also preferably used. be able to.

<First transparent electrode>
As the first transparent electrode 4, all the electrodes that can be normally used for the organic EL element 1 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 metals and ITO, ZnO, TiO ₂ and An oxide semiconductor such as SnO ₂ can be given.

  Preferably, a metal that is not an oxide is preferable, and among them, a metal containing silver as a main component is preferable. In this case, as shown in FIG. 2, the first transparent electrode 4 has a two-layer structure in which a base layer 4b and an electrode layer 4a formed thereon are sequentially laminated from the transparent substrate 2 side. preferable. Among these, the electrode layer 4a is a layer formed using, for example, silver or an alloy containing silver as a main component, and the base layer 4b is, for example, at least one kind of atom selected from a nitrogen atom and a sulfur atom. It is preferable that it is a layer containing the organic compound which has.

  Note that the transparency of the first transparent electrode 4 means that the light transmittance at a light wavelength of 550 nm is 50% or more. The main component in the electrode layer 4a means that the content in the electrode layer 4a is 98% by mass or more.

(1) Underlayer The underlayer 4b is a layer provided on the transparent substrate 2 side of the electrode layer 4a. The material constituting the base layer 4b is not particularly limited as long as it can suppress the aggregation of silver when forming the electrode layer 4a 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. Further, it is allowed to mix a compound having no nitrogen atom and sulfur atom within a range that does not inhibit the effect of the underlayer 4b.

  When the underlayer 4b 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, it is possible to make the underlayer 4b uniform, exhibit the above-described effect (suppression of silver aggregation) as the underlayer, and make the thin silver electrode layer uniform.

  When the underlayer 4b 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 4b, it is sufficient if the base layer 4b is formed with a necessary layer thickness that allows uniform film formation.

  As a method for forming the underlayer 4b, a wet process such as a coating method, an inkjet 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 that can be applied to the formation of the underlayer will be described.

(1-1) Organic Compound Having Nitrogen Atom An 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. A compound having a large interaction with the 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 is not involved in aromaticity among the unshared electron pairs possessed by the nitrogen atoms constituting the compound.

  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 4b 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 molecular weight M of the mixed compound. The number n of effective 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]. A range is preferable.

Hereinafter, as the low molecular weight organic compound having a nitrogen atom constituting the underlayer 4b, the above-described exemplary compound No. 1 having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more is used. 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.

  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.

(1-2) Polymer having a nitrogen atom In the present invention, a polymer can also 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).

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.

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 in the range 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 each 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 formula (P1) 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 preferably used for 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 in the range whose weight average molecular weights are 1000-1 million.

  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.

(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 and the like in the molecule. Among these, it is preferable to have a sulfide bond or a mercapto group. These organic compounds having a sulfur atom are described, for example, in JP-A No. 2009-163177.

  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, a calibration curve (also referred to as calibration curve) is created, and the measurement target (This was used to calculate the weight average molecular weight of the product. Here, the weight average molecular weight of the polystyrene used in the sample was set at approximately equal intervals.)

(2) Electrode layer The electrode layer 4a 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 4b.

  As a method of forming such an electrode layer 4a, 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, etc. And a method using the dry process. Among these, the vapor deposition method is preferably applied.

  In addition, the electrode layer 4a is formed on the base layer 4b, so that the electrode layer 4a is sufficiently conductive without high-temperature annealing after the electrode layer 4a 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 4a 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 4a as described above may have a structure in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  Further, the electrode layer 4a preferably has a thickness in the range of 5 to 30 nm. When the thickness is less than 30 nm, the absorption component or reflection component of the layer is small, and the transmittance of the first transparent electrode 4 is increased. In addition, when the thickness is greater than 5 nm, sufficient conductivity of the layer can be ensured. Preferably it is the range of 6-20 nm, More preferably, it is the range of 6-15 nm.

  The first transparent electrode 4 having a laminated structure composed of the base layer 4b and the electrode layer 4a formed thereon is covered with a protective film at the top of the electrode layer 4a. The electrode layer 4a may be laminated. In this case, it is preferable that the protective film and the other electrode layer 4a have light transmittance so that the light transmittance of the first transparent electrode 4 is not impaired.

(3) Effect of first transparent electrode The first transparent electrode 4 having the above-described configuration is, for example, an underlayer formed using an organic compound having at least one atom selected from a nitrogen atom and a sulfur atom. The electrode layer 4a made of silver or an alloy containing silver as a main component is provided on 4b. Thereby, when the electrode layer 4a is formed on the base layer 4b, silver atoms constituting the electrode layer 4a interact with a compound containing nitrogen atoms or sulfur atoms constituting the base layer 4b. As a result, the distance at which silver atoms diffuse on the surface of the underlayer 4b decreases, and as a result, aggregation of silver is suppressed.

  Here, in general, in the formation of the electrode layer 4a containing silver as a main component, a thin film is grown by a nucleus growth type (Volume-Weber: VW type), and therefore silver particles are easily isolated in an island shape. For this reason, when the thickness of the electrode layer 4a is reduced, it is difficult to obtain conductivity, and consequently, the sheet resistance value is increased. Therefore, in order to ensure conductivity, it is necessary to increase the thickness of the electrode layer 4a. However, if the thickness is increased, the light transmittance is lowered, so that it is not suitable as the first transparent electrode 4.

  However, according to the 1st transparent electrode 4 which concerns on this invention, as above-mentioned, aggregation of silver is suppressed on the base layer 4b. For this reason, in the film formation of the electrode layer 4a made of silver or an alloy containing silver as a main component, a thin film is grown by a single-layer growth type (Frank-van der Merwe: FM type).

  Here, the transparency of the first transparent electrode 4 means that the light transmittance at a light wavelength of 550 nm is 50% or more. However, each of the materials used as the underlayer 4b is made of silver or silver. Compared with the electrode layer 4a made of an alloy as a main component, the film has a sufficiently good light transmittance. On the other hand, the conductivity of the first transparent electrode 4 is ensured mainly by the electrode layer 4a. Therefore, as described above, the electrode layer 4a made of silver or an alloy containing silver as a main component has a smaller thickness and the conductivity is ensured, thereby improving the conductivity of the first transparent electrode 4. It is possible to achieve both the improvement of the light transmission and the light transmission. Further, by providing the base layer 4b, the color purity of the organic EL element 1 in the non-light emitting region can be improved.

  Furthermore, since the first transparent electrode 4 according to the present invention can be adjusted to be thin in a range in which specular light reflection at the silver electrode does not occur, it can contribute to an improvement in light emission luminance.

<Second transparent electrode>
The second transparent electrode 12 is an electrode film that functions as a cathode for supplying electrons to the organic light emitting layer, and a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof are used.

As with the first transparent electrode 4, all the electrodes that can be normally used for the organic EL element 1 can be used as the second transparent electrode 12. Specifically, aluminum, silver, magnesium, lithium, magnesium / same mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture and rare earth metals and ITO, ZnO, TiO ₂ and An oxide semiconductor such as SnO ₂ can be given.

  Especially, it is preferable that the 2nd transparent electrode 12 is a layer comprised using the alloy which has silver or the silver as a main component like the 1st transparent electrode 4. FIG.

  As a method for forming the second transparent electrode 12, 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, or the like. And a method using a dry process such as a method. Among these, the vapor deposition method is preferably applied.

  Examples of the alloy mainly composed of silver (Ag) constituting the second transparent electrode 12 include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium. (AgIn) etc. are mentioned.

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

  The second transparent electrode 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 second transparent electrode 12 preferably has a layer thickness in the range of 5 to 30 nm. When the layer thickness is less than 30 nm, the absorption component or reflection component of the layer is small, and the transmittance of the second 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.

In the present invention, the first transparent electrode 4 and the second transparent electrode 12 are preferably metal thin films. Thereby, the color of the non-light-emitting region and the non-light-emitting region can be brought close to the color in which the sealing member is colored. Further, when the sealing member 105 is colored black, reflection of external incident light by the metal layer included in the organic EL layer can be suppressed.
Moreover, in this invention, it is preferable that the shape of the 1st transparent electrode 4 and the 2nd transparent electrode 12 differs from the shape of the light emission pattern of an organic electroluminescent element. That is, the first transparent electrode 4 and the second transparent electrode 12 are not limited to the shape of the light emission pattern, and can be formed in various shapes. As a result, for example, the first transparent electrode 4 and the second transparent electrode 12 can be formed in a solid shape close to the shape of the transparent substrate, and as a result, the organic electroluminescence element in the light emitting and non-light emitting regions can be formed. Since the color can be made uniform regardless of the shape of the light emitting pattern, an effect of improving the appearance can be obtained.
Moreover, in this invention, the 1st transparent electrode 4 and the 2nd transparent electrode 12 are produced using silver (Ag), and the organic EL element 1 of a non-light-emission area | region and a non-light-emission area | region is made into black with high color purity. This is preferable.

<Electrode protective layer>
In the present invention, as shown in FIG. 3, the electrode protection layer 12 a containing an organic or inorganic compound is laminated on the second transparent electrode 12 to smooth the surface of the second transparent electrode 12, and This is preferred because it provides sufficient mechanical protection. Further, by containing an organic or inorganic compound, when the sealing member 105 is laminated, the sealing strength is increased due to solid sealing.

  The electrode protective layer 12a preferably has flexibility, and a thin polymer film or a thin metal film can be used. The organic compound used in the base layer 4b or the organic light emitting layer can be used. It is also preferable that the layer is appropriately selected and formed by the coating method or the vapor deposition method.

  The electrode protective layer 12a according to the present invention preferably contains a metal oxide from the viewpoint of solid encapsulation, and a specific example of the metal oxide includes molybdenum oxide.

  The preferred layer thickness of the electrode protective layer 12a according to the present invention can be appropriately set according to the purpose, but is preferably in the range of about 10 nm to 10 μm, for example, in the range of about 15 nm to 1 μm. Is more preferable and it is still more preferable that it is the range of 20-500 nm.

<Extraction electrode>
The extraction electrode is for electrically connecting the first transparent electrode 4 and the second transparent electrode 12 and an external power source, and the material thereof is not particularly limited, and a known material can be preferably used. For example, a metal film such as a MAM electrode (Mo / Al · Nd alloy / Mo) having a three-layer structure can be used.

<Auxiliary electrode>
The auxiliary electrode is provided for the purpose of reducing the resistance of the first transparent electrode 4 and the second transparent electrode 12, and is provided in contact with the electrode layer 4a of the first transparent electrode 4 and the electrode layer 4a of the second transparent electrode 12. It is done. 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.

<Sealing member>
The sealing member 105 of the organic EL element 1 of the present invention is used for sealing the organic EL element 1, is at least partially colored, and has at least a sealing substrate 105a and an adhesive layer 105b. In this embodiment, the sealing member 105 is comprised from the sealing base material 105a and the contact bonding layer 105b. In addition, the sealing member 105 is laminated on the surface of the laminated body 13 on the second transparent electrode 12 side through the adhesive layer 105b.
The sealing member 105 is laminated so as to seal the stacked body 13 in close contact.

  The sealing substrate 105a is not particularly limited and may be a known one. Specific examples include a glass plate, a polymer plate / film, a metal plate / metal foil / film, and the like. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of 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.

In addition, a polymer film or a metal film can be preferably used because the organic EL element 1 can be thinned. Furthermore, the polymer film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less and a water vapor permeability of 1 × 10 ⁻³ g / (m ² · 24 h) or less. Preferably there is. Further, it is more preferable that the oxygen permeability is 1 × 10 ⁻⁵ ml / (m ² · 24 h · atm) or less and the water vapor permeability is 1 × 10 ⁻⁵ / (m ² · 24 h).

Further, in the present invention, it is preferable that the sealing base material 105a includes, as a constituent element, an aluminum foil in which at least one surface (alumite-treated surface) has been subjected to alumite treatment.
As a result, the durability under a high temperature and high humidity environment is improved, and the sealing substrate 105a is colored black, so that reflection of external incident light by the metal layer included in the organic EL layer can be suppressed. it can.

  The alumite treatment can be usually carried out in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, sulfamic acid, etc., but is preferably carried out in a sulfuric acid bath. The alumite treatment in the sulfuric acid bath is preferably performed under the conditions of a sulfuric acid concentration of 100 to 200 g / l, an aluminum ion concentration of 1 to 10 g / l, a liquid temperature of 20 ° C., and an applied voltage of about 20V. The average film thickness of the alumite-treated film is usually preferably 20 μm or less, and more preferably 10 μm or less.

  Further, the sealing substrate 105a may be one colored with a known colorant described later, for example, an aluminum foil whose surface is colored with carbon black, pigment blue, or the like is preferably used. it can. Thereby, the color of the non-light-emitting region and the non-light-emitting region can be various colors.

  Specific examples of the adhesive layer 105b (adhesive) include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing such as 2-cyanoacrylates. Examples thereof include an adhesive such as a mold. Moreover, the heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In the present invention, it is particularly preferable that the adhesive layer 105b contains a colorant. The colorant may be a known one and may be a pigment or a dye as long as it can be dispersed or dissolved in the adhesive layer 105b, and is not particularly limited.

Specific examples of the known colorant applicable to the sealing member (sealing substrate and adhesive layer) according to the present invention include, for example, black colorant, carbon black, magnetic substance, iron / titanium composite An oxide black or the like can be used. Examples of the carbon black include channel black, furnace black, acetylene black, thermal black, and lamp black. Examples of the magnetic material include ferrite and magnetite.
The yellow colorant includes C.I. as a dye. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc., and C.I. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185, etc. can be used, and mixtures thereof can also be used.
Further, as a colorant for magenta, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, etc. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122, 139, 144, 149, 166, 177, 178, 222, etc. can be used. Mixtures of these can also be used.
Cyan coloring agents include C.I. as a dye. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc. I. Pigment Blue 1, 7, 15, 15, 60, 62, 66, 76, etc. can be used, and a mixture thereof can also be used.

  The content of the colorant is preferably in the range of 0.5 to 20% by mass in the adhesive layer 105b.

  In addition, as a coloring agent, since the effect which suppresses reflection of the external incident light by the metal layer contained in an organic electroluminescent layer is acquired, it is more preferable to use black pigments, such as carbon black.

Moreover, since the organic EL element 1 may be deteriorated by the heat treatment, it is preferable that the adhesive can be cured from room temperature (25 ° C.) to 80 ° C. Further, a desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print it like screen printing.
Further, a barrier layer may be provided between the second transparent electrode 12 or the electrode protective layer 12 a and the sealing member 105. In the present invention, the barrier layer is not included in the sealing member 105.
As the material of the barrier layer, any inorganic material having a function of suppressing the intrusion of elements such as moisture and oxygen may be used. For example, silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, zirconium oxide Etc. can be used.
As the characteristics of the barrier layer, the water vapor transmission rate is about 0.01 g / [m ² · day · atm] or less, preferably the water vapor transmission rate is about 0.001 g / [m ² · day · atm] or less, and the resistivity is 1. It is preferable that the gas barrier property and the insulating property be 10 × 10 ¹² Ω · cm or more.
The barrier layer can be formed by, for example, vacuum deposition, sputtering, magnetron sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD. A method such as a method, a laser CVD method, or a thermal CVD method is used.
In addition, although the layer thickness of a barrier layer is suitably set according to conditions, 100-1000 nm is preferable.

≪Method for manufacturing organic EL element≫
The manufacturing method of the organic EL element 1 having a laminate in which at least a transparent substrate, a first transparent electrode, an organic layer, and a second transparent electrode are laminated in this order and a sealing member according to the present invention includes at least hole injection as an organic layer. An organic layer forming step of forming a layer, a hole transport layer, a light emitting layer, and a sealing step of laminating a sealing member colored at least partially on the laminate from the surface on the second transparent electrode side It is the manufacturing method of this. Thereby, the manufacturing method of the organic electroluminescent element which has high flexibility and can change the color of the non-light-emitting region and the non-light-emitting region into various colors can be provided.

  Moreover, in the manufacturing method of the said organic EL element 1 of this invention, an organic layer formation process differs at least one layer of a positive hole injection layer, a positive hole transport layer, and a light emitting layer from a 1st transparent electrode or a 2nd transparent electrode. It is preferable to form in a shape. That is, the first transparent electrode and the second transparent electrode are not limited to the shape of the light emission pattern, and may be formed in various shapes. Thereby, for example, the first transparent electrode and the second transparent electrode can be formed in a shape close to the shape of the transparent substrate and solid, and as a result, the color of the organic electroluminescence element in the light emitting and non-light emitting regions can be changed. Since it can be made uniform regardless of the shape of the light emitting pattern, an effect that the appearance can be improved is obtained.

  Furthermore, in the manufacturing method of the organic EL element 1 of the present invention, after laminating the sealing member on the laminated body by the sealing step, at least a part of the laminated body is irradiated with ultraviolet rays to emit a light emitting pattern. It is preferable to have the process (light irradiation process) of forming. As a result, since the light emitting region emits light with respect to the non-light emitting region of black or the like, there is an effect that it is possible to obtain a visual effect that the formed light emission pattern appears to rise up with respect to the non light emitting region. can get.

  Here, the “light emission pattern” refers to a design (pattern or pattern in the figure), characters, images, etc. displayed by the organic EL element 1.

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

(1) Lamination process In the manufacturing method of the organic EL element 1 of this embodiment, the 1st transparent electrode 4, the organic layer 6, and the 2nd transparent electrode 12 are laminated | stacked on the transparent substrate 2, and the laminated body 13 which concerns on this invention. A step of forming (lamination step) is performed.
This stacking step includes an organic layer forming step of forming at least a hole injection layer, a hole transport layer, and a light emitting layer as the organic layer 6.

  First, a transparent substrate 2 is prepared, and a desired electrode material, for example, a thin film made of a material for the first transparent electrode 4 is formed on the transparent substrate 2 to a thickness of 1 μm or less, preferably 10 to 200 nm. In this way, the first transparent electrode 4 is produced by forming the film by a method such as vapor deposition or sputtering. At the same time, an extraction electrode connected to an external power source is formed at the end of the first transparent electrode 4 by an appropriate method such as vapor deposition.

(Organic layer formation process)
In the organic layer forming step in the present embodiment, at least a hole injection layer, a hole transport layer, and a light emitting layer are formed on the first transparent electrode 4 in this order as the organic layer 6. In addition, the organic layer 6 of this embodiment shall be comprised from a positive hole injection layer, a positive hole transport layer, a light emitting layer, and an electron carrying layer.

The formation of each of these layers includes spin coating, casting, inkjet, vapor deposition, and printing, but vacuum vapor deposition is easy because a homogeneous layer is easily obtained and pinholes are difficult to generate. The method or spin coating method is particularly preferred. Further, different 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 the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is 1 × 10 ⁻⁶ to 1 × 10. Each condition is appropriately selected 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. Is desirable.

  After the organic light emitting layer is formed as described above, the second transparent electrode 12 is formed thereon by an appropriate forming method such as a vapor deposition method or a sputtering method. At this time, the second transparent electrode 12 is patterned in a shape in which a terminal portion is drawn from the upper side of the organic layer 6 to the periphery of the transparent substrate 2 while being insulated from the first transparent electrode 4 by the organic layer 6. .

When forming the stacked body 13, a shadow mask may be appropriately selected and used so that a light emission pattern is formed.
In this case, the same shadow mask may be used when forming each layer of the stacked body 13, or may be used only when forming any one layer. The shadow mask is preferably used when forming the hole injection layer and the electron injection layer because the contrast of the light emission pattern (both during light emission and during non-light emission) can be increased. More preferably, it is used only when forming the injection layer.
In addition, the formation of the light emission pattern is not limited to the method of forming the stacked body 13 using this shadow mask. For example, after forming a layer for which the light emission pattern is to be formed, a known photolithography method or the like is used. May be.

(2) Sealing Step After the stacking step, a step (sealing step) for sealing the organic EL element 1 is performed.
In the sealing step of the present invention, the organic EL element 1 is sealed by laminating at least a part of the sealing member 105 colored on the laminate 13 from the surface on the second transparent electrode 12 side.
In other words, the surface of the laminated body 13 on the second transparent electrode 12 side is solid-contact sealed with a sealing member 105 that is at least partially colored.

(3) Light irradiation process The light irradiation process in this embodiment modulates the light emission function of the organic EL element 1 by irradiating at least a part of the laminate 13 with ultraviolet rays (light irradiation), and forms a light emission pattern. It is a process.
Here, modulating the light emitting function by light irradiation means changing the light emitting function of the organic EL element 1 by changing the function of a hole transport material or the like constituting the organic EL element 1 by light irradiation. Say.

  In the manufacturing method of the organic EL element 1 of the present invention, the light irradiation step includes laminating the sealing member 105 on the laminate 13 in the sealing step, and then applying ultraviolet rays to at least a part of the laminate 13. A step of forming a light emission pattern by irradiation is preferable. As a result, since the light emitting region emits light with respect to the non-light emitting region of black or the like, there is an effect that it is possible to obtain a visual effect that the formed light emission pattern appears to rise up with respect to the non light emitting region. can get.

In the light irradiation step, the light irradiation method may be any method as long as the predetermined pattern region of the organic layer 6 is irradiated with predetermined light so that the irradiated portion can be changed to a light emitting region or a non-light emitting region whose luminance has changed. It may be present and is not limited to a specific method.
The light irradiated in the light irradiation step may further contain ultraviolet rays, visible rays or infrared rays, but preferably contains ultraviolet rays.
Here, in the present invention, ultraviolet rays refer to electromagnetic waves having a wavelength longer than that of X-rays and shorter than the shortest wavelength of visible light, and specifically those having a wavelength in the range of 1 to 400 nm.

  Ultraviolet generation means and irradiation means are not particularly limited as long as they are generated and irradiated by a conventionally known apparatus or the like. Specific examples of the light source include a high-pressure mercury lamp, a low-pressure mercury lamp, a hydrogen (deuterium) lamp, a rare gas (xenon, argon, helium, neon, etc.) discharge lamp, a nitrogen laser, and an excimer laser (XeCl, XeF, KrF, KrCl). Etc.), hydrogen lasers, halogen lasers, various harmonics of visible (LD) -infrared lasers (THG (Third Harmonic Generation) light of YAG lasers) and the like.

  Such a light irradiation process is preferably performed after the sealing process.

  Further, in the light irradiation step, by adjusting the light intensity or the irradiation time and changing the light irradiation amount, it is possible to change the light emission luminance of the light irradiation portion according to the light irradiation amount. The greater the light irradiation amount, the lower the emission luminance, and the smaller the light irradiation amount, the smaller the emission luminance attenuation rate. Therefore, when the light irradiation amount is 0, that is, when no light is irradiated, the light emission luminance is maximum. Further, by sufficiently performing light irradiation, the light emission luminance can be set to 0, that is, a non-light emitting region.

  As described above, the organic EL element 1 having a desired light emission pattern can be manufactured. In the production of such an organic EL element 1, it is preferable that the organic layer 6 to the second transparent electrode 12 are consistently produced by a single evacuation, but the transparent substrate 2 is taken out from the vacuum atmosphere on the way, and is different. A forming method may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

In addition, when a direct current voltage is applied to the organic EL element 1 obtained in this way, light emission occurs when a voltage in the range of about 2 to 40 V is applied to the first transparent electrode 4 and the second transparent electrode 12. Can be observed. Further, an AC voltage may be applied, and the AC waveform to be applied may be arbitrary.
At this time, since the current flows only in the light emitting pattern portion, the power consumption can be reduced as compared with the LED that guides light to the unnecessary portion.

  Moreover, after forming a light emission pattern using a shadow mask, a light emission pattern can be formed more precisely by performing light irradiation.

≪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, since the organic EL element of the present invention is a top emission type, when used in a display device, the contrast is high and excellent display performance can be realized.

  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, "part by mass" or "mass%" is represented.
Note that all the organic EL elements 101 to 109 manufactured in this example have a light emission pattern formed by the light emitting region 21 shown in FIGS. 4A to 4C. In addition, unless otherwise specified below, the laminate and the sealing member include the transparent substrate 2 (solid line), the first transparent electrode 4 (dotted line), the organic layer 6 (one-dot chain line), the first shown in FIGS. 2 It shall be formed in the shape represented by the transparent electrode 12 (broken line) and the sealing member 105 (solid line). In addition, 6a in FIG. 4B represents any one layer of the organic layer 6 as mentioned later.

<< Production of Organic EL Element 101 >>
(Preparation of transparent substrate)
As a flexible transparent base material, a commercially available polyethylene terephthalate film (PET film) base material (thickness 125 μm) is selected, and on the base material, referring to Example 1 of JP2012-116101A, A gas barrier layer was formed.

Specifically, UV curing organic / inorganic manufactured by JSR Corporation on one side of a polyester film (Teijin DuPont Films Co., Ltd., ultra-low heat yield PET Q83) having a width of 500 mm and a thickness of 125 μm that is easily bonded on both sides. Hybrid hard coat material OPSTAR Z7535 was applied so that the layer thickness after application and drying was 4 μm, and then curing conditions: 1.0 J / cm ² , in an air atmosphere, using a high-pressure mercury lamp, drying conditions: 80 ° C., Curing was performed in 3 minutes to form a bleed-out prevention layer.

Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the opposite surface of the resin substrate so that the layer thickness after application and drying is 4 μm, and then drying conditions; After drying at 80 ° C. for 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a flat layer.

  The maximum cross-sectional height Rt (p) of the obtained flat layer was 16 nm with a surface roughness specified by JIS B 0601.

  The surface roughness was measured using an AFM (Atomic Force Microscope) SPI3800N DFM manufactured by SII. The measurement range for one time was 10 μm × 10 μm, the measurement location was changed, and the measurement was performed three times. The average of the Rt values obtained in each measurement was taken as the measurement value.

  The thickness of the resin base material produced as described above was 133 μm.

  Next, the first gas barrier layer is applied to the surface of the flat layer of the resin base material using a vacuum extrusion type coater so that the dry layer thickness is 150 nm. did.

  The coating solution containing the inorganic precursor compound is a non-catalytic perhydropolysilazane 20 mass% dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NN120-20) and an amine catalyst containing 5 mass% solids. Hydroamine silazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NAX120-20) is used by mixing, and after adjusting the amine catalyst to 1% by mass of solid content, it is further diluted with dibutyl ether. This was prepared as a 5% by mass dibutyl ether solution.

  After coating, the film was dried under the conditions of a drying temperature of 80 ° C., a drying time of 300 seconds, and a dew point of 5 ° C. in a dry atmosphere.

  After drying, the resin substrate was gradually cooled to 25 ° C., and the coating surface was subjected to a modification treatment by irradiation with vacuum ultraviolet rays in a vacuum ultraviolet irradiation apparatus. A Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm was used as a light source of the vacuum ultraviolet irradiation apparatus.

<Modification processing equipment>
Excimer irradiation device MODEL: MECL-M-1-200, wavelength 172 nm, manufactured by M.D.
<Reforming treatment conditions>
Excimer light intensity 3J / cm ² (172nm)
Stage heating temperature 100 ° C
Oxygen concentration in the irradiation device 1000ppm
After the modification treatment, the base material on which the gas barrier layer was formed was dried in the same manner as described above, and further subjected to the second modification treatment under the same conditions to form a gas barrier layer having a dry layer thickness of 150 nm.

  Next, in the same manner as the first gas barrier layer, a second gas barrier layer was formed on the first gas barrier layer to produce a PET film having a gas barrier layer.

  The above PET film with a gas barrier layer was cut into a size of 50 mm × 50 mm, fixed to a Teflon (registered trademark) frame (equivalent to a tension of 100 N / m), and the following operation was performed.

(Preparation of internal light extraction layer)
The organic EL element 101 did not form an internal light extraction layer, and the following first transparent electrode, second transparent electrode, and organic layer were formed directly on the PET substrate.

(Production of first transparent electrode)
As the first transparent electrode, after patterning the transparent substrate into the shape of the first transparent electrode 4 shown in FIG. 4A by photolithography, the transparent substrate with the ITO transparent electrode is ultrasonicated with isopropyl alcohol. After cleaning, drying with dry nitrogen gas, and UV ozone cleaning for 5 minutes, this transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus.
Each of the deposition crucibles in the vacuum deposition apparatus was filled with an optimal amount of the constituent material of each layer. As the evaporation crucible, a crucible made of a resistance heating material made of molybdenum or tungsten was used.

After depressurizing to a vacuum degree of 1 × 10 ⁻⁴ Pa, using a shadow mask that can be patterned into the shape of the organic layer 6 shown in FIG. 4A, the deposition crucible containing the compound M-4 is energized and heated, and the deposition rate is 0. It vapor-deposited on the transparent substrate at 1 nm / second, and provided the 15-nm-thick hole injection layer.
Next, Compound M-2 was vapor-deposited in the same manner to provide a 40 nm-thick hole transport layer.
Subsequently, using the following compound BD-1 and compound H-1, the compound BD-1 was co-deposited at a deposition rate of 0.1 nm / second so that the concentration of compound BD-1 was 5% and the concentration of compound H-1 was 95%. A fluorescent light emitting layer exhibiting blue light emission having a thickness of 15 nm was provided.
Then, using the following compound GD-1, compound RD-1 and compound H-2, the compound GD-1 has a concentration of 17%, the RD-1 has a concentration of 0.8%, and the compound H-2 has 82.2%. Co-deposited at a deposition rate of 0.1 nm / second so as to achieve a concentration of 15 nm / second, and provided a phosphorescent light-emitting layer exhibiting a yellow thickness of 15 nm.
Next, Compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a thickness of 30 nm.

Further, after an electron injection layer made of LiF was formed to a thickness of 1.5 nm, aluminum was subsequently formed to a thickness of 1 nm. Further, under a vacuum of 5 × 10 ⁻⁴ Pa, silver (Ag) is used as a material for forming the second transparent electrode, and the second transparent electrode having a thickness of 10 nm is formed by resistance heating vapor deposition so as to have an extraction electrode. Formed.

(Sealing)
Furthermore, for the laminate formed on the transparent substrate, the method described in the examples of JP-A No. 2002-319485 (the description relating to Example 1 of the present invention from paragraphs 0018 to 0022 of JP-A No. 2002-319485). The organic EL element 101 was produced by sealing the can.

<< Production of Organic EL Element 102 >>
In the production of the organic EL element 101, the organic EL element 102 was produced in the same manner except that the sealing was performed as follows.

(Sealing)
<Preparation of adhesive composition>
100 parts by weight of “OPanol B50 (manufactured by BASF, Mw: 340,000)” as polyisobutylene resin (A), and “Nisseki Polybutene Grade HV-1900 (manufactured by Nippon Oil Corporation, Mw: 1900) as polybutene resin (B) 30 parts by weight, 0.5 parts by weight of “TINUVIN 765 (manufactured by BASF Japan, having a tertiary hindered amine group)” as a hindered amine light stabilizer (C), “IRGANOX 1010 as a hindered phenol antioxidant (D)” (BASF Japan made, both β-positions of hindered phenol groups have a tertiary butyl group) 0.5 parts by weight, and cyclic olefin polymer (E) as “Eastotac H-100L Resin (Eastman Chemical Co.) ”50 parts by mass is dissolved in toluene, The solid content concentration of about 25 wt% of the adhesive composition was prepared.

<Preparation of sealing member>
First, a surface of an aluminum foil side of a 50 μm thick polyethylene terephthalate film on which an aluminum (Al) foil having a thickness of 100 μm was laminated was colored with carbon black to prepare a sealing substrate. Next, the solution of the prepared adhesive composition was applied to the aluminum side (gas barrier layer side) of the sealing substrate so that the thickness of the adhesive layer formed after drying was 20 μm. It was dried for 2 minutes to form an adhesive layer. Next, as a release sheet, a release treatment surface of a polyethylene terephthalate film subjected to a release treatment with a thickness of 38 μm was attached to the formed adhesive layer surface to produce a sealing member.

  The sealing member produced by the above-described method is prepared in a size of 40 mm × 50 mm, the release sheet is removed under a nitrogen atmosphere, dried on a hot plate heated to 120 ° C. for 10 minutes, and then lowered to room temperature. After confirming this, the organic light-emitting device was laminated so as to completely cover the cathode, and heated at 90 ° C. for 10 minutes for sealing.

<< Production of Organic EL Element 103 >>
In the production of the organic EL element 102, the organic EL element 103 was produced in the same manner except that the production of the first transparent electrode was performed as follows.

(Production of first transparent electrode)
Compound No. containing nitrogen atom 10 was placed in a resistance heating boat made of tantalum. These substrate holders and resistance heating boats were attached to 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 reducing the pressure of the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound was heated by heating, and the layer was deposited on the substrate within a deposition rate range of 0.1 to 0.2 nm / second. Compound No. 25 having a thickness of 25 nm. An underlayer composed of 10 was provided.

Next, the substrate formed up to the base layer was transferred to the second vacuum chamber while being vacuumed, and after the pressure of the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. As a result, an electrode layer made of silver having a layer thickness of 10 nm was formed within a deposition rate range of 0.1 to 0.2 nm / second. Thereby, the 1st transparent electrode by which the base layer and the electrode layer were laminated | stacked in this order was obtained.
In addition, the base layer and the electrode layer were formed using a shadow mask at the time of vapor deposition so that it might become the shape of the 1st transparent electrode 4 shown to FIG. 4A.

<< Production of Organic EL Element 104 >>
In the production of the organic EL element 103, the organic EL element 104 was similarly produced except that the sealing substrate was produced by performing black alumite treatment instead of coloring the surface on the aluminum foil side with carbon black. did.

<< Production of Organic EL Element 105 >>
In the production of the organic EL element 104, an organic EL element 105 was produced in the same manner except that 5.2 parts by mass of carbon black was added to the preparation of the pressure-sensitive adhesive composition when laminating.

<< Production of Organic EL Element 106 >>
In the production of the organic EL element 105, the light emitting layer was formed in the shape of the organic layer 6a shown in FIG. 4B using a shadow mask. The other organic layers were formed in the shape of the organic layer 6 shown in FIG. 4B. In addition, the first transparent electrode and the second transparent electrode were not formed in the shape of the light emitting region 21 but formed in a size of 50 mm × 50 mm. Except these, the organic EL element 106 was produced in the same manner.

<< Production of Organic EL Element 107 >>
In the production of the organic EL element 106, the organic EL element 107 was produced in the same manner except that the hole injection layer was formed in the shape of the organic layer 6a shown in FIG. 4B using a shadow mask instead of the light emitting layer.

<< Production of Organic EL Element 108 >>
In the production of the organic EL element 106, the organic EL element 108 was produced in the same manner except that the electron injection layer was formed in the shape of the organic layer 6a shown in FIG. 4B using a shadow mask instead of the light emitting layer.

<< Production of Organic EL Element 109 >>
In the production of the organic EL element 106, patterning is not performed when the light emitting layer is formed, and the organic EL element is similarly formed except that the light emitting region 21 shown in FIG. 4C is formed by patterning by light irradiation after sealing as described below. Element 109 was produced.

(Patterning by light irradiation)
On the surface of the transparent substrate on the light extraction side, a pattern mask and an ultraviolet absorption filter (made by Isuzu Seiko Glass Co., Ltd.) are placed under reduced pressure, and a UV tester (Iwasaki Electric Co., Ltd., SUV-W151: 100 mW / cm ² ), patterning was performed by irradiating ultraviolet rays from the substrate side for 3 hours.
In addition, the ultraviolet absorption filter used the thing with the light transmittance of a wavelength component of 320 nm or less of 50% or less (cut wavelength: 320 nm).

≪Evaluation≫
[Flexibility (bending characteristics)]
After being wound 100 times on a cylinder having a diameter of 5 cm, the luminescent image was confirmed and the area of the luminescent region was measured. The numerical values shown in Table 2 are the ratio (%) of the area of the light emitting region that is a dark spot. 30% or less is acceptable.

[Resistance under high temperature and high humidity]
Each organic EL element was stored for 300 hours in an environment of 85 ° C. and 85% RH, and then the area of the light emitting region that had become a dark spot was measured. The numerical values shown in the table are the ratio (%) of the area of the light emitting region that is a dark spot. 30% or less is acceptable.

[Measurement of color]
Measurement of color: With a CM-2600d manufactured by Konica Minolta, the color of the non-light-emitting region and the non-light-emitting region was measured in the L ^* a ^* b ^* color system.
Note that an A light source (tungsten light source) was used as the light source used for the measurement, an SCI (regular reflection light included) method was adopted as the measurement method, and the viewing angle was 2 °.
Table 2 shows the value of L ^* as the color of the light emitting region when no light is emitted. L ^* represents lightness, and when the value is 0, it means black, and when it is 100, it means white. In this embodiment, the sealing member is colored black, and the smaller L ^* is, the less reflection of external incident light is, which is preferable. Accept 25 or less.
The color misregistration was evaluated by ΔE ^* _ab calculated as follows. ΔL ^* , Δa ^*, and Δb ^* represent the color difference between the light emitting region and the non-light emitting region.
ΔE ^* _ab is less than 20 as acceptable.
ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2

  From the results shown in Table 2, it is recognized that the organic EL elements 102 to 109 are more flexible, resistant in a high temperature and high humidity environment, and have a better color when not emitting light than the organic EL element 101. It was.

  As described above, the present invention is suitable for providing an organic electroluminescence element having high flexibility and capable of changing the color of the non-light-emitting region and the non-light-emitting region to various colors and a method for manufacturing the same.

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Transparent substrate 4 1st transparent electrode 4a Electrode layer 4b Underlayer 6 Organic layer 12 2nd transparent electrode 12a Electrode protective layer 13 Laminated body 105 Sealing member 105a Sealing base material 105b Adhesive layer

Claims (7)

An organic electroluminescence element having a laminate and a sealing member in which at least a transparent substrate, a first transparent electrode, an organic layer, and a second transparent electrode are laminated in this order,
Extract light only from the transparent substrate side,
The sealing member has a capping group member having an adhesive layer, and a layer which is colored disposed only on the adhesive layer side even without low,
The laminated body is sealed by the sealing member by laminating the sealing substrate on the surface on the second transparent electrode side through the adhesive layer. Luminescence element.   The organic electroluminescence device according to claim 1, wherein the first transparent electrode and the second transparent electrode are metal thin films.   The organic electroluminescence device according to claim 1 or 2, wherein the sealing base material includes an aluminum foil subjected to an alumite treatment as a constituent element. The adhesive layer, and an organic material of the insulating as adhesives, coloring an organic electroluminescent device according to any one of claims 1 to 3, characterized in that it contains. The organic electroluminescence device according to claim 4, wherein a content ratio of the colorant is in a range of 0.5 to 20% by mass in the adhesive layer. At least a transparent substrate, a first transparent electrode, an organic layer and a second transparent electrode have a laminate as well as the sealing member are laminated in this order, a manufacturing method of an organic electroluminescent device is taken out only light from the transparent substrate side ,
As the organic layer, at least a hole injection layer, a hole transport layer, an organic layer forming step of forming a light emitting layer, and
A sealing step of laminating the the laminate, before Kifutome member from the surface of the second transparent electrode side,
I have a,
The sealing member has a sealing substrate having at least an adhesive layer, and a colored layer disposed only on the adhesive layer side,
In the sealing step of laminating the sealing member, the sealing substrate is laminated on the laminate through the adhesive layer . A method for producing an organic electroluminescent element, comprising: 7. The method according to claim 6 , further comprising: forming a light emitting pattern by irradiating at least a part of the laminated body with ultraviolet rays after laminating the sealing member on the laminated body in the sealing step. method of manufacturing an organic electroluminescent device according to.

Images