JP5857754B2 - ORGANIC ELECTROLUMINESCENT ELEMENT, METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE - Google Patents

Description

The present invention relates to an organic electroluminescent element, a method for manufacturing an organic electroluminescent element, a display device, and a lighting device.

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. The device emits light by utilizing the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability.

  However, in organic EL elements for practical use in the future, development of organic EL elements that emit light efficiently and with high luminance with lower power consumption is desired.

  Since the publication of an organic EL device using phosphorescence emission from an excited triplet from Princeton University (MA Baldo et al., Nature, 395, 151-154 (1998)), phosphorescence at room temperature Research on materials that exhibit this has become active. For example, M.M. A. Baldo et al. , Nature, 403, 17, 17, 750-753 (2000).

  When the excited triplet is used, the upper limit of the internal quantum efficiency is 100%. In principle, the luminous efficiency is four times that of the excited singlet, and there is a possibility that almost the same performance as a cold cathode tube can be obtained. Therefore, it is attracting attention as a lighting application.

Many compounds have been studied mainly for heavy metal complexes such as iridium complexes. In addition, studies using tris (2-phenylpyridine) iridium as a dopant have been made. In addition, L2Ir (acac) as a dopant, for example, (ppy) ₂ Ir (acac), tris (2- (p-tolyl) pyridine) iridium (Ir (ptpy) ₃ ), tris (benzo [h] quinoline) iridium ( Studies using Ir (bzq) ₃ ) and the like are being conducted. These metal complexes are generally called orthometalated iridium complexes. In addition, L abbreviated as described above represents a ligand, acac represents acetylacetone, ppy represents phenylpyridine, ptpy represents p-tolylpyridine, and bzq represents benzo [h] quinoline.

  In addition, attempts have been made to form devices using various iridium complexes.

  Furthermore, in order to obtain high luminous efficiency, a hole transporting compound is used as a phosphorescent compound host, and various electron transporting materials are used as phosphorescent compound hosts, and these are doped with a novel iridium complex. The use is also disclosed.

  In either case, the light emission brightness and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element.

  As described above, it is difficult for phosphorescent highly efficient light-emitting materials to shorten the light emission wavelength and improve the light emission lifetime of the device, and the performance that can withstand practical use cannot be sufficiently achieved.

  Regarding wavelength shortening, introduction of electron-withdrawing groups such as fluorine atoms, trifluoromethyl groups, and cyano groups into phenylpyridine as substituents, and introduction of picolinic acid and pyrazabole-based ligands as ligands It is known.

  However, with these ligands, the emission wavelength of the light-emitting material is shortened to achieve blue, and a high-efficiency device can be achieved. On the other hand, the light-emitting lifetime of the device is greatly deteriorated, so an improvement in the trade-off is required. It was.

  It is disclosed that a metal complex having phenylpyrazole as a ligand is a light emitting material having a short emission wavelength.

  Furthermore, a metal complex formed from a ligand having a partial structure in which a 6-membered ring is condensed to a 5-membered ring of phenylpyrazole is disclosed.

  In addition, in U.S. Patent Application Publication No. 2006/251923, International Publication No. 2007/097149, and International Publication No. 2007/097153, an iridium complex having a ligand having a phenylimidazole skeleton is used. It is disclosed that it is useful as a light-emitting dopant in organic EL devices.

  However, organic EL devices using conventionally disclosed light emitting dopants are still insufficient in terms of light emission efficiency, driving voltage, and lifetime. In the light emitting layer of the organic EL device, the light emitting dopant may be uniformly dispersed in the host compound due to problems such as carrier transportability, concentration quenching due to aggregation of the light emitting dopant, and quenching due to interaction between excitons. Although desirable, there has not yet been found a material that solves the above problems and exhibits sufficient device performance.

  As described above, many light emitting materials have been studied for synthesis mainly on iridium complexes and platinum complexes. From the viewpoint of providing an organic EL device having high light emission efficiency, low driving voltage, and long life. It is still insufficient and further solutions are being sought.

  Furthermore, as described in, for example, Japanese Patent Application Laid-Open No. 2002-302671 or International Publication No. 2007/006380, a wet method (wet process or the like) is required due to demands for large area, low cost, and high productivity. Can be formed at a lower temperature than the vacuum process, which can reduce the damage to the underlying organic layer, and has high expectations for improving luminous efficiency and device life. It is sent.

  In these documents, wet film formation using an ionic metal complex is realized. However, in order to realize wet film formation in an organic EL element using blue phosphorescence emission, from a practical point of view, currently known luminescent materials have solubility in solvents, solution stability, and driving voltage. In terms of device life, etc., it was still inadequate, and it was found that development of further improved technology is essential.

  On the other hand, as one of the means for improving the emission lifetime of the organic electroluminescent material, the search for the host compound and the dopant compound used in the light emitting layer has been conducted for a long time, and a structure that can be practically used is being found. . However, small changes in the structure of these compounds have a large effect on the light emission lifetime of the device, and many problems remain to be solved.

  In addition, as a means for improving the light emission lifetime of the organic electroluminescence element, it is described in Patent Document 1 and Patent Document 2 that a fluorine-containing compound is used in the light emitting layer, and a certain effect has been obtained. The level needed further improvement. In addition, when a wet process is used as a method for manufacturing an organic electroluminescence element, there is a high possibility that moisture will be mixed into the organic layer, and as a result, the tendency of shortening the lifetime of the element is recognized. Development is anxious.

International Publication No. 2011/103953 Specification JP 2004-28881A

The present invention has been made in view of the above problems, and the problem to be solved is an organic electroluminescence element having improved power efficiency, excellent emission lifetime and stability over time, a method for producing the same , and a display device using the same And providing a lighting device.

The present inventor has proceeded with extensive study in view of the above problems, an organic electroluminescent device, between an anode and a cathode, has a plurality of organic layers including a light emitting layer, the formula to the light emitting layer ( 1) and a metal complex compound having an alkyl group having 2 or more carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom as a substituent , and the organic layer adjacent to the light emitting layer An organic electroluminescence device that has improved power efficiency by having at least one layer containing a fluorine atom-containing compound, and has excellent power efficiency stability (stable with time) after storage under a light emitting life and high temperature environment. As a result, the present invention has been found.

  That is, the above problem of the present invention is solved by the following means.

1. Between an anode and a cathode, an organic electroluminescent device having a plurality of organic layers including a light emitting layer, the compound represented by the following general formula (1) to the light emitting layer, and at least one hydrogen atom as a substituent An organic electro, comprising a metal complex compound having an alkyl group having 2 or more carbon atoms substituted with a fluorine atom , and at least one of organic layers adjacent to the light emitting layer contains a fluorine atom-containing compound Luminescence element.

〔式中、Ａは酸素原子、硫黄原子またはＮ−Ｒ^９を表し、Ｒ^１〜Ｒ^９は各々水素原子または置換基を表し、Ｒ^１〜Ｒ^９の少なくとも一つはフッ素原子またはフッ素原子含有置換基を表す。〕

[Wherein, A represents an oxygen atom, a sulfur atom or N—R ⁹ , R ^{1 to} R ⁹ each represents a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁹ contains a fluorine atom or a fluorine atom. Represents a substituent. ]

2 . In the compound represented by the general formula (1), at least one of R ¹ to R ^9, and wherein the number of carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom is 2 or more alkyl groups der Rukoto 2. The organic electroluminescence device according to item 1 .
3. 3. The compound represented by the general formula (1), wherein the alkyl group is an alkyl group having 4 or more carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Organic electroluminescence element.
4). In the compound represented by the general formula (1), A is an oxygen atom, The organic electroluminescence device according to any one of Items 1 to 3, wherein A is an oxygen atom.

5 . The organic electroluminescent element according to any one of claims 1 to 4, wherein the compound represented by the general formula (1) or the metal complex compound has a fluorine atom-substituted aromatic group. .

6 . All the organic layers adjacent to the said light emitting layer contain the said fluorine atom containing compound, The organic electroluminescent element as described in any one of Claim 1-5 characterized by the above-mentioned.

7). It is a manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element as described in any one of Claims 1-6,
At least one layer of, method of manufacturing the organic electroluminescent device you characterized that you formed by a wet coating method organic layer.

8). The organic electroluminescence device according the first term to any one of paragraph 6, characterized in that the white light emission.

9. A display device comprising the organic electroluminescence element according to any one of Items 1 to 6 and Item 8.

10. An organic electroluminescence element according to any one of items 1 to 6, and 8, comprising: an illuminating device.

By the above means of the present invention, it is possible to provide an organic electroluminescence element with improved power efficiency and excellent emission lifetime and stability over time, a method for producing the same, a display device and a lighting device using the same.

It is a schematic diagram which shows an example of the display apparatus comprised from the organic EL element of this invention. It is a schematic diagram of the display part A which comprises the display apparatus shown in FIG. It is the schematic of the illuminating device of this invention. It is a schematic diagram of the illuminating device of this invention.

The organic electroluminescence device of the present invention is an organic electroluminescence device having a plurality of organic layers including a light emitting layer between an anode and a cathode, wherein the light emitting layer is a compound represented by the general formula (1) at least , And a metal complex compound having an alkyl group having 2 or more carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom as a substituent , and at least one organic layer adjacent to the light emitting layer contains a fluorine atom It is characterized by including a compound. This feature is a technical feature common to the inventions according to claims 1 to 10 .

  As an embodiment of the present invention, it is preferable that the light emitting layer further contains a metal complex compound substituted with a fluorine atom, from the viewpoint of further manifesting the effect of the present invention. The compound represented by the general formula (1) or the metal complex compound substituted with a fluorine atom preferably has a fluorine atom-substituted alkyl group or a fluorine atom-substituted aromatic group. Furthermore, it is preferable that the compound represented by the general formula (1) or the metal complex compound substituted with a fluorine atom has a structure having a fluorine atom-substituted aromatic group. Moreover, it is preferable that all the organic layers adjacent to the said light emitting layer contain the said fluorine atom containing compound. In addition, forming at least one of the organic layers by a wet coating method is one of the preferred embodiments from the viewpoint of more manifesting the intended effect of the present invention.

  Conventionally, as described in Patent Document 1 and Patent Document 2, the use of a fluorine-containing compound in the light-emitting layer as one of means for improving the light emission lifetime of the organic electroluminescent material is utilized. Was known. However, it is still insufficient to achieve high quality characteristics such as power efficiency, light emission lifetime, and stability over time, which are currently required for organic electroluminescence elements. In particular, when considering the production efficiency of the organic electroluminescence element, it is an effective means to form the organic layer by a wet coating method, but in the methods described in the above patent documents, the formed organic layer It has been found that moisture may remain inside, and as a result, the light emission lifetime and the like of the organic electroluminescence element deteriorate due to the influence of the remaining moisture.

  As a result of intensive studies to achieve the above object, the present inventors have found that a compound containing at least a fluorine atom represented by the general formula (1) (host) as the light emitting layer constituting the organic electroluminescence device (host) Compound) and at least one of the organic layers adjacent to the light emitting layer is also made to contain a fluorine atom-containing compound, thereby improving the power efficiency and improving the light emission life and stability over time. The dramatic effect that an organic electroluminescent element can be obtained was discovered. In particular, the above-described effect was remarkably exhibited when the organic layer was formed using the wet coating method. That is, by applying a fluorine atom-containing compound to the light emitting layer constituting the organic layer and at least one layer adjacent thereto, the hydrophobic effect of fluorine atoms can be effectively expressed and the object of the present invention is achieved. I guess that was made.

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

<< Constituent layers of organic EL elements >>
In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode // hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode Buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode In the organic EL device of the present invention, the light emitting layer contains at least the compound represented by the general formula (1), and At least one of the organic layers adjacent to the light emitting layer contains a fluorine atom-containing compound More preferably, the light-emitting layer contains a compound represented by the general formula (1) and a metal complex compound substituted with a fluorine source at the same time.

  In the configurations (i) to (viii) above, the organic layer adjacent to the light emitting layer refers to an electron transport layer, a hole transport layer, a hole blocking layer, and an anode buffer layer.

  The light emitting layer according to the present invention may form a light emitting layer unit by forming a unit. Further, a non-light emitting intermediate layer may be provided between the light emitting layers, and the intermediate layer may include a charge generation layer. The organic EL element of the present invention preferably emits white light and is preferably a lighting device using these.

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

<Light emitting layer>
As described above, the light emitting layer according to the present invention contains at least a compound (host compound) containing a fluorine atom represented by the general formula (1). With the compound represented by (1), conventionally known host compounds and dopants can be used in combination as long as the effects of the present invention are not impaired. In particular, all the materials of the light emitting layer are generally used. It is a preferable aspect that it is composed of a compound containing a fluorine atom represented by formula (1) (host compound) and a metal complex compound (luminescent dopant) substituted with a fluorine atom.

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

  The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 5 to 100 nm.

  For the production of the light emitting layer, a light emitting dopant and a host compound described later are used, for example, vacuum deposition method, wet coating method (also called wet process, for example, spin coating method, casting method, die coating method, blade coating method, roll coating method). , An ink-jet method, a printing method, a spray coating method, a curtain coating method, an LB method (including Langmuir-Blodgett method))) and the like. In the present invention, it is particularly preferable to form a light emitting layer by applying a wet coating method (wet process) from the viewpoint that the effects of the present invention can be exhibited.

  The light emitting layer of the organic EL device of the present invention contains at least a light emitting host compound which is a compound represented by the general formula (1). More preferably, together with the compound represented by the general formula (1), a light emitting dopant compound which is a metal complex compound substituted with a fluorine atom (phosphorescent dopant (also referred to as phosphorescent dopant or phosphorescent dopant group)) And a fluorescent dopant).

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

  At least one of the light emitting hosts used in the light emitting layer according to the present invention is a compound containing a fluorine atom represented by the general formula (1).

In the general formula (1), A represents an oxygen atom, a sulfur atom or N—R ⁹ , R ^{1 to} R ⁹ each represents a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁹ is a fluorine atom. Or represents a fluorine atom-containing substituent.

  The fluorine atom-containing substituent in the general formula (1) according to the present invention is preferably a fluorinated hydrocarbon group, and more preferably a fluorine atom substituted alkyl group or a fluorine atom substituted aromatic group.

  Examples of the fluorine-substituted alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group, and a perfluoro group. An octadecyl group etc. are mentioned.

  Examples of the fluorine atom-substituted aromatic group include a fluorobenzene group, a 2-fluorinated phenyl group, a 3-fluorinated phenyl group, a 4-fluorinated phenyl group, and a 2,3,5,6-fluorinated phenyl group. 2,3,4,5,6-fluorinated phenyl group.

Examples of other substituents represented by R ^{1 to} R ⁹ include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, Tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.) , Aromatic hydrocarbon groups (also called aromatic hydrocarbon ring groups, aromatic carbocyclic groups, aryl groups, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group , Azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group Biphenylyl group), aromatic heterocyclic group (for example, pyridyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1, 2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, A quinolyl group, a benzofuryl group, a dibenzofuryl group, a benzothienyl group, a dibenzothienyl group, an indolyl group, a carbazolyl group, an azacarbazolyl group (any one or more of the carbon atoms constituting the carbazole ring of the carbazolyl group is replaced by a nitrogen atom) Quinoxalinyl) , Pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio Group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (Eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, , Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group) Group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Cetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy groups ( For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonyl) Amino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl Sulfonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, Cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethyl) Ureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pi Lysylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group) Group), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenyl) Sulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butyl) Mino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (for example, chlorine atom, bromine atom etc.), cyano group, nitro group, Examples thereof include a hydroxy group, a mercapto group, a silyl group (for example, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a phenyldiethylsilyl group), a phosphono group, and the like. Among these, an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are particularly preferable.

  Moreover, these substituents may be further substituted with the above-mentioned substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

  Although the exemplary compounds H-101 to H-130 are shown below as the compounds represented by the general formula (1), the present invention is not limited to these exemplified compounds.

  The light emitting layer according to the present invention is used in a conventional organic EL device together with the compound containing a fluorine atom represented by the general formula (1) according to the present invention within a range not impairing the intended effect of the present invention. A host compound can be used. Typically, a carbazole derivative, a triarylamine derivative, an aromatic derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, an oligoarylene compound or the like having a basic skeleton, or a carboline derivative or a diazacarbazole derivative (here And the diazacarbazole derivative represents one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom.

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

  By using a plurality of types of light-emitting hosts, the movement of charges can be adjusted, and the organic EL element can be made highly efficient.

  Moreover, it becomes possible to mix different light emission by using multiple types of well-known compounds used as a phosphorescent dopant mentioned later, and can thereby obtain arbitrary luminescent colors.

  The light-emitting host that can be used in combination with 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 (polymerization). Light emitting host), and one or more of such compounds may be used.

  Specific examples of the known light-emitting host include compounds described in the following documents.

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

  Hereinafter, specific examples of conventionally known host compounds that can be used with the compound containing a fluorine atom represented by the general formula (1) according to the present invention in the light emitting layer according to the organic EL element of the present invention will be given. The present invention is not limited to these.

[Luminescent dopant compound]
A light-emitting dopant compound (also referred to as a light-emitting dopant) will be described.

  In the metal complex compound substituted with a fluorine atom according to the present invention, the group substituted with a fluorine atom is preferably a fluorinated hydrocarbon group, more preferably a fluorine atom-substituted alkyl group or a fluorine atom-substituted aromatic group. It is preferable that

  Examples of the fluorine-substituted alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group, and a perfluoro group. An octadecyl group etc. are mentioned.

  Examples of the fluorine atom-substituted aromatic group include a fluorobenzene group, a 2-fluorinated phenyl group, a 3-fluorinated phenyl group, a 4-fluorinated phenyl group, and a 2,3,5,6-fluorinated phenyl group. 2,3,4,5,6-fluorinated phenyl group.

  Examples of the luminescent dopant that is a metal complex compound substituted with a fluorine atom according to the present invention include a fluorescent dopant (also referred to as a fluorescent compound), a phosphorescent dopant (phosphorescent material, phosphorescent compound, phosphorescent compound). Etc.) can also be used.

(Phosphorescent dopant)
The phosphorescent dopant (also referred to as phosphorescent dopant) according to the present invention will be described.

  The phosphorescent dopant compound according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

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

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

  As a light-emitting dopant relating to the organic EL device of the present invention, it is one of preferred embodiments to use a metal complex compound substituted with a fluorine atom, but the present invention is within a range not impairing the intended effect of the present invention. A metal complex compound conventionally used in an organic EL device can be used together with the metal complex compound substituted with a fluorine atom, and examples thereof include compounds described in the following patent publications.

  For example, International Publication No. 00/70655, JP 2002-280178, JP 2001-181616, JP 2002-280179, JP 2001-181617, JP 2002-280180, JP 2001-247859 A, JP 2002-299060 A, JP 2001-313178 A, JP 2002-302671 A, JP 2001-345183 A, JP 2002-324679 A, International Publication. No. 02/15645, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-2002 A. No. 117978, Japanese Patent Application Laid-Open No. 2002-33858 JP, JP-A-2002-170684, JP-A-2002-352960, WO01 / 93642, JP-A-2002-50483, JP-A-2002-1000047, JP-A-2002-173684. JP-A-2002-359082, JP-A-2002-175484, JP-A-2002-363552, JP-A-2002-184582, JP-A-2003-7469, JP-A-2002-525808, JP 2003-7471, JP 2002-525833, JP 2003-31366, JP 2002-226495, JP 2002-234894, JP 2002-2335076, JP 2002 No. 2411751, JP 2001-319779 A. JP, 2001-319780, 2002-62824, 2002-100474, 2002-203679, 2002-343572, 2002-203678, etc. It is.

(Fluorescent dopant (also called fluorescent compound))
As fluorescent dopants, 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, and compounds having a high fluorescence quantum yield such as laser dyes.

  In addition, the light-emitting dopant according to the present invention may be used in combination of a plurality of types of compounds, or may be a combination of phosphorescent dopants having different structures, or a combination of a phosphorescent dopant and a fluorescent dopant.

  Hereinafter, exemplary compounds D-101 to D-140 are shown as metal complex compounds substituted with fluorine atoms according to the present invention, but the present invention is not limited to these exemplified compounds.

  Moreover, although the specific example of the conventionally well-known light emission dopant which can be used together with the said metal complex compound substituted by the said fluorine atom which concerns on this invention as a light emission dopant below is given, this invention is not limited to these. .

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

  An electron transport material (including a hole blocking material and an electron injection material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer. Can be selected and used from conventionally known compounds.

  Examples of conventionally known materials used for the electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, And azacarbazole derivatives including carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives, and the like.

  Here, the azacarbazole derivative refers to one in which one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom.

  Furthermore, in the 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. It is also possible to use a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain.

  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 the terminal substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material.

  Further, similarly to the hole injection layer and the hole transport layer, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.

  The electron transport layer is made of an electron transport material such as a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an ink jet method, a printing method, or a spraying method. The film can be formed by a coating method, a curtain coating method, an LB method (such as Langmuir-Blodgett method)), etc. In particular, a wet coating method (wet process) ) To form an electron transport layer.

  Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, about 5-5000 nm, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, at least one of the organic layers adjacent to the light emitting layer contains a fluorine atom-containing compound. In one embodiment, the electron transport layer is disposed at a position adjacent to the light emitting layer. Sometimes, an electron transport material containing a fluorine atom can be used as the electron transport material.

  Hereinafter, exemplary compounds ET-101 to ET-110 are shown as electron transport materials containing fluorine atoms according to the present invention, but the present invention is not limited to these exemplified compounds.

本発明に係る電子輸送層においては、本発明の目的とする効果を損なわない範囲で、本発明に係る上記フッ素原子を含有する電子輸送材料と共に、従来有機ＥＬ素子で用いられる電子輸送材料を用いることができる。

In the electron transport layer according to the present invention, the electron transport material conventionally used in the organic EL element is used together with the electron transport material containing the fluorine atom according to the present invention within a range not impairing the intended effect of the present invention. be able to.

  Hereinafter, although the specific example of the conventionally well-known compound (electron transport material) preferably used for formation of the electron carrying layer of the organic EL element of this invention is given, this invention is not limited to these.

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

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.

  For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

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

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

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

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. In particular, it is preferable to form the hole transport layer by applying a wet coating method (wet process).

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

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

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

  In the present invention, at least one of the organic layers adjacent to the light-emitting layer contains a fluorine atom-containing compound, but when the hole transport layer is disposed at a position adjacent to the light-emitting layer, one embodiment As the hole transport material, a hole transport material containing a fluorine atom can be used.

  Although the exemplary compounds HT-101 to HT-110 are shown below as hole transport materials containing fluorine atoms according to the present invention, the present invention is not limited to these exemplified compounds.

また、本発明に係る正孔輸送層においては、本発明の目的とする効果を損なわない範囲で、本発明に係る上記フッ素原子を含有する正孔輸送材料と共に、従来有機ＥＬ素子で用いられる正孔輸送材料を用いることができる。

In addition, in the hole transport layer according to the present invention, a positive electrode used in a conventional organic EL device together with the hole transport material containing the fluorine atom according to the present invention is within a range that does not impair the intended effect of the present invention. A hole transport material can be used.

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

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.

  Moreover, the structure of the above-mentioned electron transport layer can be used as a hole-blocking layer according to the present invention, if necessary.

  The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  When the hole blocking layer is provided adjacent to the light emitting layer, as one embodiment, a hole blocking material containing a fluorine atom can be used as the hole blocking material.

  Examples of the hole blocking material containing a fluorine atom that can be applied to the hole blocking layer include a compound containing a fluorine atom represented by the general formula (1) that can be applied to the light emitting layer. .

  Moreover, as a hole blocking material other than a hole blocking material containing a fluorine atom, carbazole derivatives and azacarbazole derivatives (herein, azacarbazole derivatives) cited as the conventionally known host compounds similarly described in the light emitting layer , Preferably represents one in which one or more carbon atoms constituting the carbazole ring are replaced by a nitrogen atom).

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode.

  Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.

  (1) Keywords using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), which is molecular orbital calculation software manufactured by Gaussian, USA. As a value (eV unit converted value) calculated by performing structure optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

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

  Moreover, the structure of the above-mentioned hole transport layer can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron blocking layer according to the present invention is preferably 3 to 100 nm, and more preferably 3 to 30 nm.

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

  In the organic EL device of the present invention, when the injection layer is disposed at a position adjacent to the light emitting layer, as one aspect, the injection layer can contain a fluorine atom-containing compound.

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

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

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

  In addition, the materials used for the anode buffer layer and the cathode buffer layer can be used in combination with other materials. For example, the materials can be mixed in the hole transport layer or the electron transport layer.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used.

  When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.

Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

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

《Support substrate》
The support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent.

  Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · MPa) or less and a water vapor permeability of 1 × 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

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

  The method for forming the 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 weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.

  Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

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

<< Method for Manufacturing Organic EL Element >>
As an example of a method for producing an organic EL device, a device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode Will be described.

  First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable substrate so as to have a thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode.

  Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, or a cathode buffer layer, which is an element material, is formed thereon.

  In the organic EL device of the present invention, it is preferable that at least the cathode and the electron transport layer adjacent to the cathode are coated and formed by a wet coating method.

  Wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but precise thin films can be formed. From the viewpoint of high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable. Different film forming methods may be applied for each layer.

  Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) can be used.

  Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as ultrasonic dispersion, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm, and provided as a cathode, thereby obtaining a desired organic EL device. .

  Further, the order can be reversed, and the cathode, cathode buffer layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order.

  When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. 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 the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.

Furthermore, the polymer film has a oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · MPa) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, 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 addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. 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 like screen printing.

  In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.

  Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials.

  The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, 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, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, etc.), among others, anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

  In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

  The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

  However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

  At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

  The arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL element of the present invention is processed to provide, for example, a microlens array-like structure on the light extraction side of the substrate, or in combination with a so-called condensing sheet, so that the organic EL element is in front of the element light emitting surface By condensing in the direction, the luminance in a specific direction can be increased.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.

  As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (Konica Minolta Sensing Co., Ltd.) is applied to the CIE chromaticity coordinates.

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

<Display device>
The display device of the present invention will be described. The display device of the present invention comprises the organic EL element of the present invention.

  Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.

  In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.

  The configuration of the organic EL element provided in the display device is selected from the above-described configuration examples of the organic EL element as necessary.

  Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect | mode of manufacture of the organic EL element of said invention.

  In the case of applying a DC voltage to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

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

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

  Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. The present invention is not limited to these examples.

  Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below.

  In the drawing, the light L emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated Not)

  When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.

  Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.

《Lighting device》
The lighting device of the present invention will be described. The illumination device of the present invention has the organic EL element.

  The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However, It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).

  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. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

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

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

  It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved.

  According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

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

<< One Embodiment of Lighting Device of the Present Invention >>
One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.

  The non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material. LC0629B) is applied, and this is overlaid on the cathode to be in close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and as shown in FIG. 3 and FIG. Can be formed.

  FIG. 3 is a schematic view of the lighting device, and the organic EL element 101 of the present invention is covered with a glass cover 102. The sealing operation with the glass cover is performed in a glove box (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere.

  4 shows a cross-sectional view of the lighting device. In FIG. 4, reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

  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 "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

  First, the structures of the compounds used in the examples are shown below.

* 1: ADS254BE (American Dye Source, Inc. hole transport material, Poly [N, N-bis (4-butylphenyl) -N, N-bis (phenyl) -benzidine])
Example 1
<< Production of organic EL element >>
[Production of Organic EL Element 1-1]
This ITO transparent electrode is provided after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which a film of ITO (Indium Tin Oxide) with a thickness of 100 nm is formed on a glass substrate of 100 mm × 100 mm × 1.1 mm. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes to produce an anode.

  This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of copper phthalocyanine (CuPc) is put into a molybdenum resistance heating boat, and α-NPD (hole transport material) is put into another molybdenum resistance heating boat. 200 mg, 200 mg of CBP (host compound) is put into another molybdenum resistance heating boat, 200 mg of Exemplified Compound D-9 is added as a dopant compound to another molybdenum resistance heating boat, and BCP is put into another molybdenum resistance heating boat. 200 mg of (electron transport material) was added and attached to a vacuum deposition apparatus.

Next, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, heated by energizing the heating boat containing CuPc, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second to form a 10 nm hole injection layer. Was provided.

  Further, the heating boat containing α-NPD was energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second to provide a 30 nm hole transport layer.

  Next, the heating boat containing CBP and the heating boat containing Exemplary Compound D-9 were heated by applying electricity to the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively. A 40 nm light-emitting layer was formed.

  Next, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 30 nm electron transport layer.

  Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 110nm was vapor-deposited, the cathode was formed, and the blue light emission organic EL element 1-1 which formed each component layer with the vapor deposition method was produced.

[Production of Organic EL Elements 1-2 to 1-103]
In the production of the organic EL device 1-1, the types of the dopant compound and the host compound, the type of the electron transport material, and the type of the hole transport material used in forming the light emitting layer are shown in Table 1, Table 2, and Table 3, respectively. Blue-emitting organic EL elements 1-2 to 1-103 were produced in the same manner except that the combination was changed.

<< Evaluation of organic EL elements >>
[Production of lighting device]
The non-light-emitting surface of each of the organic EL elements prepared above is covered with a glass cover, and an epoxy-based photocurable adhesive (as a sealant around the glass cover side where the glass cover and the glass substrate on which the organic EL element is manufactured contacts) Using Lax Track LC0629B, manufactured by Toagosei Co., Ltd., this is superimposed on the cathode side of the organic EL element and brought into close contact with the transparent support substrate, and UV light is irradiated to the portion of the glass substrate side excluding the organic EL element. It hardened and sealed, and the illuminating devices 1-1 to 1-103 which consist of a structure shown in FIG.3 and FIG.4 were produced.

[Evaluation of lighting equipment]
The following evaluations were performed on each of the manufactured illumination devices.

(Evaluation of power efficiency)
Using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.), the front luminance and luminance angle dependency of the organic EL elements constituting each lighting device are measured, and the power efficiency at the front luminance of 1000 cd / m ² is obtained. It was.

  In addition, evaluation of power efficiency was displayed by the relative value which sets the power efficiency of the organic EL element 1-1 to 100. The larger the value, the better the power efficiency.

(Evaluation of luminous lifetime)
Each lighting device performs continuous light emission under a constant current condition of ^2.5 mA / cm ² in an environment of 23 ° C. and 50% RH, and using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing). The time (half-life: τ1 / 2) required to reach half the initial luminance was measured. In addition, evaluation of the light emission lifetime was displayed by the relative value which sets the half life (time) of the organic EL element 1-1 to 100. The larger the value, the longer the light emission lifetime.

(Evaluation of stability over time)
Each lighting device was stored for 24 hours in a high temperature environment of 60 ° C., and then each power efficiency before and after high temperature storage was determined, and a power efficiency ratio was determined according to the following formula, which was used as a measure of stability over time. The larger the numerical value (%), the better the stability over time.

Stability over time (%) = Power efficiency after storage at high temperature / Power efficiency before storage at high temperature x 100
In addition, the measurement of power efficiency was calculated | required similarly to the method described in the said evaluation of power efficiency.

(Check the emission color)
About each illuminating device, the light emission color at the time of performing continuous light emission on ^2.5 mA / cm < ² > constant current conditions was determined visually.

  The results obtained as described above are shown in Table 1, Table 2, and Table 3.

  As is clear from the results shown in Tables 1, 2 and 3, at least one organic layer adjacent to the light emitting layer containing the compound represented by the general formula (1) as the material for forming the light emitting layer. The blue light-emitting organic EL element (illumination device) of the present invention having a structure containing a fluorine atom-containing compound in the layer has characteristics excellent in power efficiency, light emission lifetime, and temporal stability compared to the comparative example. I understand that.

  Furthermore, the above-described effect can be achieved by having the light emitting layer contain the compound represented by the general formula (1) and the metal complex compound substituted with a fluorine atom at the same time, or all layers (electrons) adjacent to the light emitting layer. It was confirmed that the fluorine-containing compound was contained in the transport layer and the hole transport layer), so that it was more effectively expressed.

Example 2
<< Production of organic EL element >>
[Production of Organic EL Element 2-1]
In the production of the organic EL device 1-1 described in Example 1, green light emission was performed in the same manner except that Exemplified Compound D-1 was used instead of Exemplified Compound D-9 which is a dopant compound used in the light emitting layer. Organic EL element 2-1 was prepared.

[Production of Organic EL Elements 2-2 to 2-12]
In preparation of the said organic EL element 2-1, except having changed the kind of dopant compound and host compound which are used by formation of a light emitting layer, the kind of electron transport material, and the kind of hole transport material into the combination of Table 4, respectively. Similarly, green-emitting organic EL elements 2-2 to 2-12 were produced.

<< Evaluation of organic EL elements >>
In the same manner as in the method described in Example 1, lighting devices 2-1 to 2-12 were produced using the produced organic EL elements.

  Next, for the produced organic EL element and lighting device, evaluation and confirmation of power efficiency, light emission lifetime, stability over time (%) and light emission color were performed in the same manner as described in Example 1 and obtained. The results are shown in Table 4.

  In addition, about the power efficiency of Table 4, and the light emission lifetime, each characteristic value of the organic EL element 2-1 was set to 100, and it displayed as a relative value.

  As is clear from the results shown in Table 4, the light emitting layer forming material contains at least the compound represented by the general formula (1) and the fluorine atom-containing compound in the organic layer adjacent to the light emitting layer. It turns out that the organic EL element (illuminating device) of the green light emission of this invention which consists of a structure has the characteristic excellent in power efficiency, the light emission lifetime, and temporal stability with respect to the comparative example.

Example 3
<< Production of organic EL element >>
[Production of Organic EL Element 3-1]
In the production of the organic EL device 1-1 described in Example 1, red light emission was performed in the same manner except that Exemplified Compound D-6 was used instead of Exemplified Compound D-9 which is a dopant compound used in the light emitting layer. Organic EL element 3-1 was prepared.

[Production of Organic EL Elements 3-2 to 3-12]
In preparation of the said organic EL element 3-1, except having changed the kind of dopant compound and host compound which are used by formation of a light emitting layer, the kind of electron transport material, and the kind of hole transport material into the combination of Table 5, respectively. Similarly, red light emitting organic EL elements 3-2 to 3-12 were produced.

<< Evaluation of organic EL elements >>
In the same manner as in the method described in Example 1, lighting devices 3-1 to 3-12 were manufactured using the organic EL elements manufactured as described above.

  Next, for the produced organic EL element and lighting device, evaluation and confirmation of power efficiency, light emission lifetime, stability over time (%) and light emission color were performed in the same manner as described in Example 1 and obtained. The results are shown in Table 5.

  In addition, about the power efficiency of Table 5, and the light emission lifetime, each characteristic value of the organic EL element 3-1 was set to 100, and it displayed as a relative value.

  As is clear from the results shown in Table 5, at least the compound represented by the general formula (1) was contained as a material for forming the light emitting layer, and the fluorine atom-containing compound in the organic layer adjacent to the light emitting layer was contained. It turns out that the organic EL element (illuminating device) of the red light emission of this invention which consists of a structure has the characteristic excellent in power efficiency, the light emission lifetime, and temporal stability with respect to a comparative example.

Example 4
<< Preparation of organic EL element: Forming organic layer by wet coating method >>
[Production of Organic EL Element 4-1]
This ITO transparent electrode is formed by patterning a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing ITO (indium tin oxide) with a thickness of 100 nm on a 100 mm × 100 mm × 1.1 mm glass substrate. The transparent support substrate provided with was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes to produce an anode.

  Next, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water is used on the transparent support substrate. A thin film was formed by spin coating under conditions of 3000 rpm and 30 seconds, and then dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 20 nm.

  Subsequently, the transparent support substrate provided with the first hole transport layer was transferred to a nitrogen atmosphere, and 50 mg of ADS254BE (manufactured by American Dye Source, Inc.) was added to 10 ml of monochlorobenzene on the formed first hole transport layer. A thin film was formed by spin coating under the conditions of 2500 rpm and 30 seconds. Furthermore, it vacuum-dried at 130 degreeC for 1 hour, and the 2nd positive hole transport layer was formed.

  On this second hole transport layer, a thin film was formed by spin coating under conditions of 1000 rpm and 30 seconds using a solution in which 100 mg of CBP and 13 mg of Exemplified Compound D-9 were dissolved in 10 ml of butyl acetate. . Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and formed the light emitting layer with a film thickness of about 45 nm.

  Next, a thin film was formed on this light emitting layer by spin coating under a condition of 1000 rpm and 30 seconds using a solution of 50 mg of BCP dissolved in 10 ml of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and formed the electron carrying layer with a film thickness of about 25 nm.

Next, this substrate is fixed to a substrate holder of a vacuum deposition apparatus, the vacuum chamber is decompressed to 4 × 10 ⁻⁴ Pa, potassium fluoride 0.4 nm is deposited as a cathode buffer layer, and aluminum 110 nm is further deposited. A cathode was formed, and a blue light-emitting organic EL element 4-1 was produced.

[Production of Organic EL Elements 4-2 to 4-103]
In the production of the organic EL element 4-1, the types of the dopant compound and the host compound, the type of the electron transport material, and the type of the hole transport material used in forming the light emitting layer are shown in Table 6, Table 7, and Table 8, respectively. Blue-emitting organic EL elements 4-2 to 4-103 were produced in the same manner except that the combination was changed.

<< Evaluation of organic EL elements >>
[Production of lighting device]
The non-light-emitting surface of each of the organic EL elements prepared above is covered with a glass cover, and an epoxy-based photocurable adhesive (as a sealant around the glass cover side where the glass cover and the glass substrate on which the organic EL element is manufactured contacts) Using Lax Track LC0629B, manufactured by Toagosei Co., Ltd., this is superimposed on the cathode side of the organic EL element and brought into close contact with the transparent support substrate, and UV light is irradiated to the portion of the glass substrate side excluding the organic EL element. It hardened and sealed, and the illuminating devices 4-1 to 4-103 which consist of a structure shown in FIG.3 and FIG.4 were produced.

[Evaluation of lighting equipment]
The following evaluations were performed on each of the manufactured illumination devices.

(Evaluation of external extraction quantum efficiency (EQE))
The organic EL element constituting each lighting device is allowed to emit light at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and light emission luminance (L) [cd / m ² immediately after the start of light emission. The external extraction quantum efficiency (EQE) was calculated.

  Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance. The external extraction quantum efficiency (EQE) is expressed as a relative value where the EQE of the organic EL element 4-1 is 100. It represents that it is excellent in external extraction quantum efficiency (EQE), so that a numerical value is large.

(Evaluation of luminous lifetime)
Each lighting device performs continuous light emission under a constant current condition of 6.0 mA / cm ² in an environment of 23 ° C. and 50% RH, and using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing). The time (half-life: τ1 / 2) required to reach half the initial luminance was measured. In addition, evaluation of the light emission lifetime was displayed by the relative value which sets the half life (time) of the organic EL element 4-1 to 100. The larger the value, the longer the light emission lifetime.

(Measurement of voltage rise rate)
The initial voltage and the voltage after 50 hours were measured when driven under a constant current condition of 6 mA / cm ² . The relative value of the voltage after 50 hours with respect to the initial voltage was determined according to the following formula, and this was used as the voltage increase rate.

Voltage rise rate (%) = voltage after 50 hours / initial voltage × 100
(Luminescent color)
About each illuminating device, the light emission color at the time of performing continuous light emission on ^2.5 mA / cm < ² > constant current conditions was determined visually.

  The results obtained as described above are shown in Table 6, Table 7, and Table 8.

  As is clear from the results described in Table 6, Table 7, and Table 8, at least the organic layer adjacent to the light emitting layer contains at least the compound represented by the general formula (1) as the light emitting layer forming material. The blue light-emitting organic EL element (illumination device) of the present invention, in which each organic layer is formed by a wet coating method with a structure containing a fluorine atom-containing compound in one layer, has a power efficiency, a light emission lifetime, and a lapse of time compared to the comparative example. It turns out that it has the characteristic which was excellent in stability.

  Furthermore, the above-described effect can be achieved by having the light emitting layer contain the compound represented by the general formula (1) and the metal complex compound substituted with a fluorine atom at the same time, or all layers (electrons) adjacent to the light emitting layer. It was confirmed that the fluorine-containing compound was contained in the transport layer and the hole transport layer), so that it was more effectively expressed.

Example 5
<< Production of organic EL element >>
[Production of Organic EL Element 5-1]
In the production of the organic EL element 4-1 described in Example 4, green light emission was performed in the same manner except that Exemplified Compound D-1 was used instead of Exemplified Compound D-9 which is a dopant compound used in the light emitting layer. Organic EL element 5-1 was prepared.

[Production of Organic EL Elements 5-2 to 5-12]
In preparation of the said organic EL element 5-1, except having changed the kind of dopant compound and host compound which are used by formation of a light emitting layer, the kind of electron transport material, and the kind of hole transport material into the combination of Table 9, respectively. Similarly, green-emitting organic EL elements 5-2 to 5-12 were produced.

<< Evaluation of organic EL elements >>
In the same manner as in the method described in Example 4, lighting devices 5-1 to 5-12 were manufactured using the organic EL elements manufactured as described above.

  Next, with respect to the produced organic EL element and lighting device, evaluation and confirmation of external extraction quantum efficiency (EQE), light emission lifetime, voltage increase rate (%), and light emission color were performed in the same manner as described in Example 4. The results obtained are shown in Table 9.

  In addition, about the external extraction quantum efficiency (EQE) and light emission lifetime of Table 9, each characteristic value of the organic EL element 5-1 was set as 100, and it displayed as a relative value.

  As is clear from the results shown in Table 9, the light emitting layer forming material contains at least the compound represented by the general formula (1) and the fluorine atom-containing compound in the organic layer adjacent to the light emitting layer. It turns out that the organic EL element (illuminating device) of the green light emission of this invention which consists of a structure has the characteristic excellent in power efficiency, the light emission lifetime, and temporal stability with respect to the comparative example.

Example 6
<< Production of organic EL element >>
[Production of Organic EL Element 6-1]
In the production of the organic EL device 4-1 described in Example 4, red light emission was performed in the same manner except that Exemplified Compound D-6 was used instead of Exemplified Compound D-9 which is a dopant compound used in the light emitting layer. Organic EL element 6-1 was prepared.

[Production of Organic EL Elements 6-2 to 6-12]
In preparation of the said organic EL element 6-1, except having changed the kind of dopant compound used by formation of a light emitting layer, the kind of host compound, the kind of electron transport material, and the kind of hole transport material into the combination of Table 10, respectively. Similarly, organic EL devices 6-2 to 6-12 emitting red light were produced.

<< Evaluation of organic EL elements >>
In the same manner as in the method described in Example 4, lighting devices 6-1 to 6-12 were produced using the produced organic EL elements.

  Next, with respect to the produced organic EL element and lighting device, evaluation and confirmation of external extraction quantum efficiency (EQE), light emission lifetime, voltage increase rate (%), and light emission color were performed in the same manner as described in Example 4. The results obtained are shown in Table 10.

  In addition, about the external extraction quantum efficiency (EQE) and light emission lifetime of Table 10, each characteristic value of the organic EL element 6-1 was set to 100, and it displayed as a relative value.

  As is clear from the results shown in Table 10, the light emitting layer forming material contains at least the compound represented by the general formula (1) and the fluorine atom-containing compound in the organic layer adjacent to the light emitting layer. It turns out that the organic EL element (illuminating device) of the red light emission of this invention which consists of a structure has the characteristic excellent in power efficiency, the light emission lifetime, and temporal stability with respect to a comparative example.

Example 7
<< Production of organic EL element >>
[Production of Organic EL Element 7-1]
This ITO transparent electrode is formed by patterning a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing ITO (indium tin oxide) with a thickness of 100 nm on a 100 mm × 100 mm × 1.1 mm glass substrate. The transparent support substrate provided with was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes to produce an anode.

  Next, the transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, 200 mg of TPD (hole transport material) is put into a molybdenum resistance heating boat, and CBP (host compound) is put into another molybdenum resistance heating boat. 200 mg of Exemplified Compound D-9 (dopant compound: blue light emission) is put in another molybdenum resistance heating boat, and 200 mg of Exemplified Compound D-1 (dopant compound: green light emission) is put in another resistance heating boat made of molybdenum. 200 mg of Exemplified Compound D-6 (dopant compound: red light emission) was put in another molybdenum resistance heating boat, and 200 mg of BCP (electron transport material) was put in another molybdenum resistance heating boat, and attached to a vacuum deposition apparatus. .

Next, the pressure in the vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, and the heating boat containing TPD is heated by energization. The vapor deposition rate is 0.1 nm / sec. A layer was formed.

  Next, each heating boat containing CBP, Exemplified Compound D-9, Exemplified Compound D-1 and Exemplified Compound D-6 was energized and heated to deposit a deposition rate of 0.1 nm / sec, 0.025 nm / sec, 0, respectively. A light emitting layer having a film thickness of 60 nm was formed by co-evaporation on the hole transport layer at 0007 nm / second and 0.0002 nm / second.

  Next, the heating boat containing BCP was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to form a 20 nm electron transport layer.

  Then, 0.5 nm of potassium fluoride was vapor-deposited as a cathode buffer layer, and further aluminum 110nm was vapor-deposited, the cathode was formed, and the white light emission organic EL element 7-1 was produced using the vapor deposition method.

[Production of Organic EL Elements 7-2 to 7-33]
In preparation of the organic EL element 7-1, except that the types of the dopant compound and the host compound used in the formation of the light emitting layer, the type of the electron transport material, and the type of the hole transport material were changed to combinations shown in Table 11, respectively. Similarly, white light emitting organic EL elements 7-2 to 7-33 were produced.

<< Evaluation of organic EL elements >>
[Production of lighting device]
The non-light-emitting surface of each of the organic EL elements prepared above is covered with a glass cover, and an epoxy-based photocurable adhesive (as a sealant around the glass cover side where the glass cover and the glass substrate on which the organic EL element is manufactured contacts) Using Lax Track LC0629B, manufactured by Toagosei Co., Ltd., this is superimposed on the cathode side of the organic EL element and brought into close contact with the transparent support substrate, and UV light is irradiated to the portion of the glass substrate side excluding the organic EL element. It hardened and sealed, and the illuminating devices 7-1 to 7-33 which consist of a structure shown in FIG.3 and FIG.4 were produced.

[Evaluation of lighting equipment]
The following evaluations were performed on each of the manufactured illumination devices.

(Evaluation of drive voltage)
Each organic EL element was obtained by measuring a voltage when driven under a constant current condition of ^2.5 mA / cm ² in an environment of 23 ° C.

  In addition, according to the following formula, the drive voltage of the organic EL element 7-1 is shown as a relative value with the drive voltage of 100 as 100. The smaller the value, the lower the voltage can be driven.

Drive voltage (relative value) = (drive voltage of each organic EL element / drive voltage of organic EL element 7-1) × 100
(Evaluation of stability over time)
Each lighting device was stored for 24 hours in a high temperature environment of 85 ° C., and then each power efficiency before and after high temperature storage was determined, and a power efficiency ratio was determined according to the following formula, which was used as a measure of stability over time. The larger the numerical value (%), the better the stability over time.

Stability over time (%) = Power efficiency after storage at high temperature / Power efficiency before storage at high temperature x 100
The power efficiency is determined as the power efficiency at a front luminance of 1000 cd / m ² by measuring the front luminance and luminance angle dependency of each organic EL element using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing). It was.

(Luminescent color)
About each illuminating device, the light emission color at the time of performing continuous light emission on ^2.5 mA / cm < ² > constant current conditions was determined visually.

  Table 11 shows the results obtained as described above.

  As is apparent from the results shown in Table 11, at least the compound represented by the general formula (1) is contained as a material for forming the light emitting layer, and at least one organic layer adjacent to the light emitting layer contains fluorine atoms. It can be seen that the white light-emitting organic EL element (illumination device) of the present invention having a composition containing a compound has a low driving voltage and excellent temporal stability compared to the comparative example. .

Example 8
<< Production of organic EL element >>
[Production of Organic EL Element 8-1]
This ITO transparent electrode is formed by patterning a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing ITO (indium tin oxide) with a thickness of 100 nm on a 100 mm × 100 mm × 1.1 mm glass substrate. The transparent support substrate provided with was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes to produce an anode.

  Next, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water is used on the transparent support substrate. A thin film was formed by spin coating under conditions of 3000 rpm and 30 seconds, and then dried at 200 ° C. for 1 hour to form a first hole transport layer having a thickness of 20 nm.

  Next, the transparent support substrate on which the first hole transport layer was formed was transferred to a nitrogen atmosphere, and 50 mg of ADS254BE (American Dye Source, Inc.) was dissolved in 10 ml of monochlorobenzene on the first hole transport layer. A thin film was formed by spin coating using the solution at 2500 rpm for 30 seconds. Furthermore, it vacuum-dried at 130 degreeC for 1 hour, and formed the 2nd positive hole transport layer.

  Next, 100 mg of CBP, 20 mg of Exemplified Compound D-9, 0.5 mg of Exemplified Compound D-1, and 0.2 mg of Exemplified Compound D-6 were dissolved in 10 ml of butyl acetate on the second hole transport layer. A thin film was formed by spin coating using the solution at 600 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and formed the light emitting layer with a film thickness of about 70 nm.

  Next, a thin film was formed on the light emitting layer by spin coating using a solution obtained by dissolving 50 mg of BCP in 10 ml of hexafluoroisopropanol (HFIP) at 1500 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and formed the electron carrying layer with a film thickness of about 20 nm.

Subsequently, this substrate is fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, 0.4 nm of potassium fluoride is deposited as a cathode buffer layer, and further, 110 nm of aluminum is deposited. Thus, a white light-emitting organic EL element 8-1 having a cathode and an organic layer formed by a wet coating method was produced.

[Production of Organic EL Elements 8-2 to 8-33]
In the production of the organic EL element 8-1, except that the types of the dopant compound and the host compound used in the formation of the light emitting layer, the type of the electron transport material, and the type of the hole transport material are changed to the combinations shown in Table 12, respectively. Similarly, white light emitting organic EL elements 8-2 to 8-33 were produced.

<< Evaluation of organic EL elements >>
[Production of lighting device]
The non-light-emitting surface of each of the organic EL elements prepared above is covered with a glass cover, and an epoxy-based photocurable adhesive (as a sealant around the glass cover side where the glass cover and the glass substrate on which the organic EL element is manufactured contacts) Using Lax Track LC0629B, manufactured by Toagosei Co., Ltd., this is superimposed on the cathode side of the organic EL element and brought into close contact with the transparent support substrate, and UV light is irradiated to the portion of the glass substrate side excluding the organic EL element. It hardened and sealed, and the illuminating devices 8-1 to 8-33 which consist of a structure shown in FIG.3 and FIG.4 were produced.

[Evaluation of lighting equipment]
The following evaluations were performed on each of the manufactured illumination devices.

(Evaluation of external extraction quantum efficiency (EQE))
The organic EL element constituting each lighting device is allowed to emit light at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and light emission luminance (L) [cd / m ² immediately after the start of light emission. The external extraction quantum efficiency (EQE) was calculated.

  Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance. The external extraction quantum efficiency (EQE) was expressed as a relative value where the EQE of the organic EL element 8-1 was 100. It represents that it is excellent in external extraction quantum efficiency (EQE), so that a numerical value is large.

(Stability over time)
After storing the organic EL element in an environment of 60 ° C. and 70% RH for one month, each power efficiency before and after storage was determined, and each power efficiency ratio was determined according to the following formula, which was used as a measure of stability over time. .

Stability over time (%) = power efficiency after storage / power efficiency before storage x 100
In addition, power efficiency uses the spectral radiance meter CS-1000 (made by Konica Minolta Sensing), measures the front luminance and luminance angle dependence of each organic EL element, and calculates | requires the power efficiency in front luminance 1000cd / m < ² >. It was.

(Luminescent color)
About each illuminating device, the light emission color at the time of performing continuous light emission on ^2.5 mA / cm < ² > constant current conditions was determined visually.

  Table 12 shows the results obtained as described above.

  As is apparent from the results shown in Table 12, at least the compound represented by the general formula (1) is contained as a material for forming the light emitting layer, and at least one organic layer adjacent to the light emitting layer contains fluorine atoms. It can be seen that the white light-emitting organic EL element (illumination device) of the present invention having a composition containing a compound has excellent external extraction quantum efficiency (EQE) and stability over time, as compared with the comparative example. .

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line A Display part B Control part 101 Organic EL element 102 Glass cover 105 Cathode 106 Organic EL layer 107 Glass substrate with a transparent electrode 108 Nitrogen gas 109 Water catching agent 201 Glass substrate 202 ITO transparent electrode 203 Partition 204 Hole injection layer 205B, 205G, 205R Light emitting layer

Claims (10)

In the organic electroluminescent device having a plurality of organic layers including a light emitting layer between an anode and a cathode, the light emitting layer has a compound represented by the following general formula (1) and at least one hydrogen atom as a substituent. An organic electro, comprising a metal complex compound having an alkyl group having 2 or more carbon atoms substituted with a fluorine atom, and at least one of organic layers adjacent to the light emitting layer contains a fluorine atom-containing compound Luminescence element.

[Wherein, A represents an oxygen atom, a sulfur atom or N—R ⁹ , R ^{1 to} R ⁹ each represents a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁹ contains a fluorine atom or a fluorine atom. Represents a substituent. ] In the compound represented by the general formula (1), at least one of R ^{1 to} R ⁹ is an alkyl group having 2 or more carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. The organic electroluminescent element according to claim 1.   3. The compound represented by the general formula (1), wherein the alkyl group is an alkyl group having 4 or more carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Organic electroluminescence element.   In the compound represented by the general formula (1), A is an oxygen atom, The organic electroluminescent device according to any one of claims 1 to 3.   5. The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (1) or the metal complex compound has a fluorine atom-substituted aromatic group.   All the organic layers adjacent to the said light emitting layer contain the said fluorine atom containing compound, The organic electroluminescent element as described in any one of Claim 1 to 5 characterized by the above-mentioned. It is a manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element as described in any one of Claims 1-6,
At least one layer of, method of manufacturing the organic electroluminescent device you characterized that you formed by a wet coating method organic layer. The organic electroluminescent device according to any one of claims 1 to 6, characterized in that white light. Display device characterized by comprising the organic electroluminescence device according to one of claim 1 to 6, and 8. An illuminating device comprising the organic electroluminescence element according to any one of claims 1 to 6 and 8.

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