ORGANIC ELECTROLUMINESCENT ELEMENT

Abstract

The present invention is related to an organic EL element having a capping layer composed of a material having (1) a high absorption coefficient; (2) a high refractive index; (3) good stability of a thin film; (4) excellent durability; (5) excellent light resistance; and (6) no absorption in each of the wavelength regions of blue, green, and red. Since an arylamine-based material having a specific structure according to the present invention is excellent in the stability and durability of a thin film, an organic EL element in which an amine compound having a specific benzazole ring structure having a high refractive index is selected as a material having a high absorbance at a wavelength of 400 nm to 410 nm in an absorption spectrum having a concentration of 10.sup.−5 mol/L and used as a material constituting a capping layer exhibits good element characteristics.

Claims

1. An organic electroluminescent element comprising at least an anode, a hole transport layer, a luminous layer, an electron transport layer, a cathode, and a capping layer in this order, wherein a refractive index of a material of the capping layer is 1.90 or more at a wavelength of 500 nm to 570 nm; and the capping layer comprises an amine compound represented by a general formula (1), ##STR00028## wherein, in the formula, R.sub.1 to R.sub.5 may be the same or different from each other, and each represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, a fused polycyclic aromatic group which may have a substituent, or an aryloxy group which may have a substituent; when there is a plurality of R.sub.1 to R.sub.4, the neighbors may form a ring; X represents an oxygen atom, a sulfur atom, or a nitrogen atom; Y and Z represent an oxygen atom or a sulfur atom; however, when X is an oxygen atom or a sulfur atom, there is no R.sub.5 for X; Ar may be identical or different from each other, and each represents a divalent group of a hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a fused polycyclic aromatic group which may have a substituent; r.sub.1 to r.sub.3 are integers of 0 to 4; and r.sub.4 represents an integer of 0 to 3.

2. The organic electroluminescent element according to claim 1, wherein the amine compound is represented by a general formula (1a), ##STR00029## wherein, in the formula, R.sub.1 to R.sub.5, X, Y, Z, and r.sub.1 to r.sub.4 are as defined in the general formula (1).

3. The organic electroluminescent element according to claim 1, wherein, in the general formula (1), r.sub.1 to r.sub.4 are 0.

4. The organic electroluminescent element according to claim 1, wherein a thickness of the capping layer is in a range of 30 nm to 120 nm.

5. A method of producing the organic electroluminescent element according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0070] FIG. 1 is a diagram showing the structure of compounds (1-1) -(1-12) as amine compounds represented by general formulae (1) and (1a).

[0071] FIG. 2 is a diagram showing the structure of compounds (1-13) -(1-24) as amine compounds represented by general formulae (1) and (1a).

[0072] FIG. 3 is a diagram showing the structure of compounds (1-25) -(1-36) as amine compounds represented by general formulae (1) and (1a).

[0073] FIG. 4 is a diagram showing the structure of compounds (1-37) -(1-48) as amine compounds represented by general formulae (1) and (1a).

[0074] FIG. 5 is a diagram showing the structure of compounds (1-49) -(1-60) as amine compounds represented by general formulae (1) and (1a).

[0075] FIG. 6 is a diagram showing an organic EL element configuration of Examples 12 to 19 and Comparative Examples 1 to 4.

DETAILED DESCRIPTION OF THE INVENTION

[0076] The amine compound represented by the general formula (1) or (1a) in the present embodiment is a new compound having a benzoazole ring structure. The benzoazole derivative which is the main skeleton of the compound can be synthesized by a known method as described below (for example, see Non-Patent Document 4). Further, the amine compound represented by the general formula (1) or (1a) of the present embodiment can be synthesized by carrying out a coupling reaction of a synthesized halogenated benzoazole derivative and an arylamine by using a copper catalyst, a palladium catalyst, or the like. In addition, by making the halogenated benzoazole derivative into a boronic acid derivative or a boronic acid ester derivative, an amine compound represented by the above general formula (1) or (1a) of the present embodiment can be similarly synthesized by a coupling reaction of the boronic acid derivative or the boronic acid ester derivative with an halogenated arylamine (for example, see Non-Patent Documents 5 and 6).

##STR00003##

[0077] Among the amine compounds represented by the above general formula (1) or (1a), which are suitably used in the organic EL element of the present embodiment, specific examples of preferred compounds are shown in FIGS. 1 to 5, but are not limited to these compounds.

[0078] The compound represented by the general formula (1) or (1a) is purified by a column chromatography purification; an adsorptive purification by using silica gel, activated carbon, activated clay, etc.; recrystallization or crystallization by using a solvent; sublimation purification; or the like. The resulting product was identified by NMR analysis. As a physical characteristic, a melting point, a glass transition point (Tg), and a refractive index were measured. The melting point is an index of vapor deposition property, the glass transition temperature (Tg) is an index of stability of the thin film state, and the refractive index is an index of improvement of light extraction efficiency.

[0079] The melting point and the glass transition temperature (Tg) were measured by a sensitive differential scanning calorimeter (manufactured by Bulker AXS, DSC 3100 SA) using a powder.

[0080] The refractive index and extinction coefficient were measured using a spectroscopic measuring device (manufactured by Filmetrics, F10-RT-UV) by preparing a thin film having a thickness of 80 nm on a silicon substrate.

[0081] The absorbance was measured by adjusting a concentration to 10.sup.−5 mol/L in a toluene solvent. The absorption coefficient was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO, V-650) at 4 different concentrations in toluene solution: 5.0×10.sup.−6 mol/L, 1.0×10.sup.−5 mol/L, 1.5×10.sup.−5 mol/L, and 2.0×10.sup.−5 mol/L.

[0082] As a structure of the organic EL element of the present embodiment, for example, in the case of a luminous element having a top emission structure, a multilayer structure in which an anode, a hole transport layer, a luminous layer, an electron transport layer, a cathode, and a capping layer are sequentially provided on a glass substrate can be used. In addition, a multilayer structure further having a hole injection layer between the anode and the hole transport layer, a multilayer structure further having an electron blocking layer between the hole transport layer and the luminous layer, a multilayer structure further having a hole blocking layer between the luminous layer and the electron transport layer, and a multilayer structure further having an electron injection layer between the electron transport layer and the cathode can be used. In these multilayer structures, it is possible to omit or combine several organic layers. For example, the hole injection layer and the hole transport layer may be combined, the hole transport layer and the electron blocking layer may be combined, the hole blocking layer and the electron transport layer may be combined, or the electron transport layer and the electron injection layer may be combined. It is also possible to have a structure in which two or more organic layers having the same function are laminated. For example, a configuration in which two hole transport layers are stacked, a configuration in which two luminous layers are stacked, a configuration in which two electron transport layers are stacked, a configuration in which two capping layers are stacked, and the like can be used.

[0083] A total thickness of each layer of the organic EL element is preferably about 200 nm to 750 nm, and more preferably about 350 nm to 600 nm. The thickness of the capping layer is preferably from 30 nm to 120 nm, and more preferably from 40 nm to 80 nm. In this case, good light extraction efficiency can be obtained. The film thickness of the capping layer can be appropriately changed according to the type of the luminous material used for the luminous element, the thickness of the organic EL element other than the capping layer, and the like.

[0084] As the anode of the organic EL element of the present embodiment, an electrode material having a large work function such as ITO or gold is used.

[0085] As the material of the hole injection layer of the organic EL element of the present disclosure, an arylamine compound having three or more triphenylamine structures in a molecule and having a structure in which the three or more triphenylamine structures are linked by a single bond or a divalent group not containing a heteroatom, for example, a material such as a starburst type triphenylamine derivative, and various triphenylamine tetramers; a porphyrin compound represented by copper phthalocyanine; an acceptor type heterocyclic compound such as hexacyanoazatriphenylene; or a coating type polymer material can be used. As the hole injection layer, a single layer formed of these materials alone may be used, or a single layer formed by mixing two or more materials may be used. The hole injection layer may be formed by laminating layers formed of the above materials alone, by laminating layers formed by mixing the materials, or by laminating the layers formed by mixing the materials with the layers formed of the above materials alone. These materials may be formed into a thin film by a vapor deposition method, or may be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0086] As the hole transport layer of the organic EL element of the present embodiment, it is preferable to use a benzidine derivative such as N, N′-diphenyl-N, N′-di(m-tolyl)benzidine (hereinafter referred to as TPD), N, N′-diphenyl-N, N′-di (α-naphthyl)benzidine (hereinafter referred to as NPD), N, N, N′,N′-tetrabiphenylylbenzidine; 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane (hereinafter referred to as TAPC); or the like. In particular, an arylamine compound having two triphenylamine structures in a molecule and having a structure in which the two triphenylamine structures are linked by a single bond or a divalent group not containing a hetero atom is preferably used. An example of the arylamine compound includes N, N, N′,N′-tetrabiphenylylbenzidine. Further, an arylamine compound having three or more triphenylamine structures in a molecule and having a structure in which the three or more triphenylamine structures are linked by a single bond or a divalent group not containing a hetero atom are preferably used. Examples of the arylamine compound include various triphenylamine trimers and tetramers. A single layer formed of these materials alone or a single layer formed by mixing two or more materials may be used. The hole transport layer may be formed by laminating layers formed of the above materials alone, by laminating layers formed by mixing the materials, or by laminating the layers formed by mixing the materials with the layers formed of the above materials alone. As the material of the hole injection layer and the hole transport layer, a coating type polymer material such as poly(3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT)/poly (styrene sulfonate) (hereinafter referred to as PSS) may be used. These materials may be formed into a thin film by a vapor deposition method, or may be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0087] In the hole injection layer or the hole transport layer, a material which is obtained by further P-doping tris bromophenylamine hexachloroantimony or a radialene derivative in a generally used material of this layer (for example, see Patent Document 3) or a polymer compound having a structure of a benzidine derivative such as TPD in its partial structure may be used.

[0088] As the electron blocking layer of the organic EL element of the present embodiment, a carbazole derivative such as 4,4′,4″-tri(N-carbazolyl)triphenylamine (hereinafter referred to as TCTA), 9,9-bis[4-(carbazole-9-yephenyl]fluorene, 1,3-bis(carbazole-9-yl)benzene (hereinafter referred to as mCP), 2,2-bis(4-carbazole-9-ylphenyl)adamantane (hereinafter referred to as Ad-Cz), and a compound having a triarylamine structure and a triphenylsilyl group represented by 9-[4-(carbazole-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene can be used. These compounds have an electron blocking function. A single layer formed of these materials alone or a single layer formed by mixing two or more materials may be used. The electron blocking layer may be formed by laminating layers formed of the materials alone, by laminating layers formed by mixing the materials, or by laminating layers formed by mixing the materials with the layers formed of these materials alone. These materials may be formed into a thin film by a vapor deposition method, or by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0089] As the luminous layer of the organic EL element of the present embodiment, metal complexes of a quinolinol derivative such as Alq.sub.3, and in addition, various metal complexes, an anthracene derivative, a bisstyrylbenzene derivative, a pyrene derivative, an oxazole derivative, a polyparaphenylenevinylene derivative, or the like can be used. The luminous layer may be composed of a host material and a dopant material. As the host material, an anthracene derivative is preferably used. As the host material, in addition to the luminous material, a heterocyclic compound having an indole ring as a partial structure of a condensed ring, a heterocyclic compound having a carbazole ring as a partial structure of a condensed ring, a carbazole derivative, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used. As the dopant material, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, or the like can be used. And a green luminous material is particularly preferable. A single layer formed of these materials alone or a single layer formed by mixing with other materials may be used. The luminous layer may be formed by laminating layers formed of the materials alone, by laminating layers formed by mixing the materials, or by laminating the layers formed by mixing the materials with the layers formed of these materials alone.

[0090] It is also possible to use a phosphorescent emitter as the luminous material. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. For example, green phosphorescent emitters such as Ir(ppy).sub.3; blue phosphorescent emitters such as FIrpic, FIr6; red phosphorescent emitters such as Btp.sub.2Ir(acac); and the like can be used, and a green phosphorescent light emitter is particularly preferred. As the host material at this time, as a hole injecting host material and electron transporting host material, a carbazole derivative such as 4,4′-di(N-carbazolyl) biphenyl (hereinafter referred to as CBP), TCTA, or mCP can be used as the host material for hole injection/transport. As the electron transporting host material, p-bis(triphenylsilyl) benzene (hereinafter referred to as UGH2), 2,2′,2″-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (hereinafter referred to as TPBI), or the like can be used, and a high-performance organic EL element can be manufactured.

[0091] Doping the phosphorescent emitting material into the host material is preferably performed by co-deposition in a range of 1% to 30% by mass with respect to the entire luminous layer to avoid concentration quenching.

[0092] As the luminous material, it is also possible to use a material that emits delayed fluorescence, such as PIC-TRZ, CC2TA, PXZ-TRZ, 4CyIPN, CDCB derivatives (for example, see Non-Patent Document 7). These luminous materials may be formed into a thin film by a vapor deposition method, or by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0093] As the material of the hole blocking layer of the organic EL element of the present embodiment, a phenanthroline derivative such as bathocuproine (hereinafter abbreviated as BCP), a metal complex of a quinolinol derivative such as aluminum (III) bis(2-methyl-8-quinolinato)-4-phenylphenolate (hereinafter referred to as BAlq), various rare earth complexes, triazole derivatives, triazine derivatives, pyrimidine derivatives, oxadiazole derivatives, and benzoazole derivatives can be used. The compounds have a hole blocking function. These materials may also serve as materials for the electron transport layer. A single layer formed of these materials alone or a single layer formed by mixing two or more materials may be used. The hole blocking layer may be formed by laminating layers formed of the above materials alone, by laminating layers formed by mixing the materials, or by laminating the layers formed by mixing the materials with the layers formed of these materials alone. These materials may be formed into a thin film by a vapor deposition method, or by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0094] As the electron transport layer of the organic EL element, in addition to metal complexes of quinolinol derivatives such as Alp.sub.3 and B Alp, various metal complexes, triazole derivatives, triazine derivatives, pyrimidine derivatives, oxadiazole derivatives, pyridine derivatives, benzimidazole derivatives, benzoazole derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, silole derivatives, or the like can be used. A single layer may be formed of these materials, or a single layer may be formed by mixing other materials. The electron transport layer may be formed by laminating layers formed of the materials alone, by laminating layers formed by mixing the materials, or by laminating the layers formed by mixing the materials with the layers formed of these materials alone. These materials may be formed into a thin film by a vapor deposition method, or by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0095] As the electron injection layer of the organic EL element of the present embodiment, an alkali metal salt such as lithium fluoride and cesium fluoride; an alkaline earth metal salt such as magnesium fluoride; a metal complex of a quinolinol derivative such as lithium quinolinol; a metal oxide such as aluminum oxide; a metal such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), cesium (Cs); or the like can be used. The electron injection layer may be omitted in the preferred choice of electron transport layer and cathode.

[0096] Further, in the electron injection layer or the electron transport layer, a material in which a metal such as cesium is further N-doped to a material usually used for the layer can be used.

[0097] As the cathode of the organic EL element of the present disclosure, an electrode material having a low work function such as aluminum; an alloy having a lower work function such as a magnesium-silver alloy, a magnesium-calcium alloy, a magnesium-indium alloy, and an aluminum-magnesium alloy; an electrode material such as ITO and IZO; or the like can be used.

[0098] As the capping layer of the organic EL element of the present embodiment, it is preferable to use an amine compound represented by the general formula (1) or (1a). A single layer may be formed of these materials, or a single layer may be formed by mixing other materials. The capping layer may be formed by laminating layers formed of the materials alone, by laminating layers formed by mixing the materials, or by laminating the layers formed by mixing the materials with the layers formed of these materials alone. These materials may be formed into a thin film by a vapor deposition method, or by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

[0099] Although an organic EL element having a top emission structure has been described above, the present disclosure is not limited thereto. The present disclosure can be similarly applied to an organic EL element having a bottom emission structure and an organic EL element having a dual emission structure emitting light from both the top and bottom. In these cases, the electrode in the direction in which the light is extracted from the luminous element is preferably transparent or semitransparent.

[0100] The refractive index of the material constituting the capping layer is preferably larger than that of the adjacent electrode. The light extraction efficiency in the organic EL element is improved by the capping layer, and the effect is more effective when a reflectivity at an interface between the capping layer and the material in contact with the capping layer is larger, because the light interference effect is larger when the reflectivity at the interface is larger. Therefore, the refractive index of the material constituting the capping layer is preferably larger than that of the adjacent electrode, and is preferably 1.90 or more, but more preferably 2.00 or more.

[0101] As an example of the method of manufacturing the organic EL element of the present embodiment, as shown in FIG. 6, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a luminous layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9, and a capping layer 10 are deposited in this order on a glass substrate 1 in which a reflective ITO electrode, as a metal anode 2, is previously formed. The capping layer 10 includes an amine compound represented by the above general formula (1) or (1a).

EXAMPLE

[0102] Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The present invention is not limited to the following examples without departing from the scope thereof.

Example 1

[0103] <Synthesis of Exemplified Compound (1-18)>

[0104] 7.0 g of 4-(3-dibenzofuranyl) benzenamine, 16.3 g of 2-(4-bromophenyl) benzoxazole, 7.8 g of t-butoxy sodium, and 70 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.7 g of tris(dibenzylideneacetone) dipalladium (0) and 0.7 g of tri-(t-butyl)phosphine in 50% (w/v) toluene were added, and the mixture was stirred overnight under heating reflux.

[0105] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product.

[0106] A solid precipitated by crystallizing the crude product with a toluene solvent was collected to obtain 12.3 g (yield 70.6%) of yellow powder of the exemplified compound (1-18).

##STR00004##

[0107] The structure of the obtained yellow powder was identified using NMR.

[0108] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0109] δ(ppm)=8.23-8.20 (4H), 8.05-7.99 (2 H), 7.84-7.50 (10 H), 7.41-7.32 (11 H).

Example 2

[0110] <Synthesis of Exemplified Compound (1-6)>

[0111] 6.1 g of 4-(3-dibenzofuranyl) benzenamine, 15.0 g of 2-(4-bromophenyl)benzothiazole, 6.8 g of t-butoxy sodium, and 60 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.7 g of tris(dibenzylideneacetone) dipalladium (0) and 0.6 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0112] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a toluene solvent was collected to obtain 9.1 g (yield 57.1%) of yellow powder of the exemplified compound (1-6).

##STR00005##

[0113] The structure of the obtained yellow powder was identified using NMR.

[0114] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0115] δ(ppm)=8.09-8.20 (8 H), 7.94-7.91 (2 H), 7.83 (1 H), 7.72-7.61 (4 H), 7.52-7.49 (3 H), 7.42-7.30 (9 H).

Example 3

[0116] <Synthesis of Exemplified Compound (1-17)>

[0117] 5.3 g of 4-(4-dibenzofuranyl)benzenamine, 12.3 g of 2-(4-bromophenyl)benzoxazole, 5.9 g of t-butoxy sodium, and 50 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.6 g of tris(dibenzylideneacetone)dipalladium (0) and 0.5 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0118] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a toluene solvent was collected to obtain 6.8 g (yield 51.5%) of yellow powder of the exemplified compound (1-17).

##STR00006##

[0119] The structure of the obtained yellow powder was identified using NMR.

[0120] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0121] δ(ppm)=8.24-8.20 (4 H), 8.05-7.96 (4 H), 7.80-7.77 (2 H), 7.68-7.59 (4 H), 7.51-7.36 (13 H).

Example 4

[0122] <Synthesis of Exemplified Compound (1-5)>

[0123] 5.3 g of 4-(4-dibenzofuranyl)benzenamine, 13.1 g of 2-(4-bromophenyl)benzothiazole, 5.9 g of t-butoxy sodium, and 100 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.6 g of tris(dibenzylideneacetone)dipalladium (0) and 0.5 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0124] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a toluene solvent was collected to obtain 7.5 g (yield 54.15%) of yellow powder of the exemplified compound (1-5).

##STR00007##

[0125] The structure of the obtained yellow powder was identified using NMR.

[0126] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0127] δ(ppm)=8.10-7.91 (12 H), 7.68-7.64 (2 H), 7.54-7.33 (13 H).

Example 5

[0128] <Synthesis of Exemplified Compound (1-19)>7.0 g of 4-(2-dibenzofuranyl)benzenamine, 16.3 g of 2-(4-bromophenyl) benzoxazole, 7.8 g of t-butoxy sodium, and 70 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.7 g of tris(dibenzylideneacetone)dipalladium (0) and 0.7 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0129] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a toluene solvent was collected to obtain 9.9 g (yield 56.9%) of yellow powder of the exemplified compound (1-19).

##STR00008##

[0130] The structure of the obtained yellow powder was identified using NMR.

[0131] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0132] δ(ppm)=8.24-8.19 (5 H), 8.05-8.02 (1 H), 7.80-7.58 (9 H), 7.54-7.49 (1 H), 7.43-7.32 (11 H).

Example 6

[0133] <Synthesis of Exemplified Compound (1-7)>

[0134] 5.0 g of 4-(2-dibenzofuranyl)benzenamine, 12.3 g of 2-(4-bromophenyl)benzothiazole, 5.6 g of t-butoxy sodium, and 50 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.5 g of tris(dibenzylideneacetone)dipalladium (0) and 0.5 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0135] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a monochlorobenzene solvent was collected to obtain 8.5 g (yield 65.0%) of yellow powder of the exemplified compound (1-7).

##STR00009##

[0136] The structure of the obtained yellow powder was identified using NMR.

[0137] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0138] δ(ppm)=8.20-8.19 (1 H), 8.09-8.03 (6 H), 7.94-7.91 (2 H), 7.75-7.61 (5 H), 7.54-7.49 (3 H), 7.43-7.30 (10 H).

Example 7

[0139] <Synthesis of Exemplified Compound (1-13)>

[0140] 5.0 g of 4-(4-dibenzothienyl) benzenamine, 11.0 g of 2-(4-bromophenyl) benzoxazole, 5.2 g of t-butoxy sodium, and 50 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.5 g of tris(dibenzylideneacetone)dipalladium (0) and 0.4 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0141] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a toluene solvent was collected to obtain 10.6 g (yield 88.2%) of yellow powder of the exemplified compound (1-13).

##STR00010##

[0142] The structure of the obtained yellow powder was identified using NMR.

[0143] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0144] δ(ppm)=8.25-8.18 (6 H), 7.91-7.88 (1 H), 7.81-7.78 (4 H), 7.63-7.49 (6 H), 7.41-7.34 (10 H).

Example 8

[0145] <Synthesis of Exemplified Compound (1-1)>

[0146] 5.0 g of 4-(4-dibenzothienyl) benzenamine, 11.6 g of 2-(4-bromophenyl)benzothiazole, 5.2 g of t-butoxy sodium, and 50 ml of toluene were added to a reaction vessel, and nitrogen gas was aerated for 30 minutes. 0.5 g of tris(dibenzylideneacetone)dipalladium (0) and 0.4 g of tri-(t-butyl) phosphine in 50% (w/v) toluene solution were added, and the mixture was stirred under heating reflux overnight.

[0147] After the reaction vessel was allowed to cool, dispersion washing was performed at 80° C., the insoluble was filtered, and the filtrate was concentrated to obtain a crude product. A solid precipitated by crystallizing the crude product with a monochlorobenzene solvent was collected to obtain 9.1 g (yield 72.22%) of yellow powder of the exemplified compound (1-1).

##STR00011##

[0148] The structure of the obtained yellow powder was identified using NMR.

[0149] The following 27 hydrogen signals were detected by .sup.1H-NMR (CDCl.sub.3).

[0150] δ(ppm)=8.24-8.18 (2 H), 8.10-8.06 (6 H), 7.94-7.88 (3 H), 7.79-7.76 (2 H), 7.63-7.49 (6 H), 7.43-7.33 (8 H).

Example 9

[0151] A melting point and a glass transition point of an amine compound represented by general formula (1) or (1a) were measured by a highly sensitive differential scanning calorimeter (manufactured by Bulker AXS, DSC 3100 SA).

TABLE-US-00001 melting glass transition point point Compound of Example 1 - ° C. 121° C. Compound of Example 2 - ° C. 119° C. Compound of Example 3 - ° C. 125° C. Compound of Example 4 - ° C. 122° C. Compound of Example 5 - ° C. 121° C. Compound of Example 6 - ° C. 118° C. Compound of Example 7 247 ° C. 127° C. Compound of Example 8 - ° C. 126° C.

[0152] The amine compound represented by the general formula (1) or (1a) has a glass transition temperature of 100° C. or higher, indicating that the thin film state is stable.

Example 10

[0153] A vapor deposited film having a thickness of 80 nm was prepared on a silicon substrate by using an amine compound represented by the general formula (1) or (1a). Regarding these prepared samples, a refractive index n at each wavelength of 400 nm, 410 nm, 500 nm, and 570 nm and an extinction coefficient k at each wavelength of 400 nm and 410 nm were measured by using a spectrometer (Filmetrics, F10-RT-UV). For comparison, comparative compounds (2-1), (2-2), (2-3), and (2-4) represented by the following structural formulae were also measured (for example, see Patent Document 4). The measurement results are summarized in Table 1.

##STR00012## ##STR00013##

TABLE-US-00002 TABLE 1 Extinction Extinction Refractive index Refractive index Refractive index Refractive index coefficient k coefficient k η (λ: 400 nm) η (λ: 410 nm) η (λ: 500 nm) η (λ: 570 nm) (λ: 400 nm) (λ: 410 nm) Exemplified Compound (1-18) 2.65 2.80 2.14 2.02 0.99 0.66 Exemplified Compound (1-6) 2.29 2.56 2.19 2.06 1.08 0.94 Exemplified Compound (1-17) 2.52 2.67 2.07 1.97 0.92 0.63 Exemplified Compound (1-5) 2.21 2.41 2.14 2.01 0.94 0.82 Exemplified Compound (1-19) 2.57 2.72 2.10 1.99 0.90 0.62 Exemplified Compound (1-7) 2.23 2.39 2.15 2.02 0.84 0.73 Exemplified Compound (1-13) 2.52 2.65 2.08 1.99 0.80 0.53 Exemplified Compound (1-1) 2.30 2.51 2.16 2.05 0.88 0.75 Comparative Compound (2-1) 2.05 2.04 1.88 1.84 0.05 0.03 Comparative Compound (2-2) 2.35 2.27 1.94 1.88 0.14 0.06 Comparative Compound (2-3) 2.30 2.20 1.91 1.87 0.45 0.31 Comparative Compound (2-4) 2.37 2.31 1.87 1.80 0.32 0.11

[0154] As described above, the compound of the present invention has a refractive index of 1.90 or higher at a wavelength of 500 nm to 570 nm, and has a value equal to or higher than that of the comparative compound, and this is expected to improve the light extraction efficiency in the organic EL element. In addition, the comparative compounds had extinction coefficients from 0.03 to 0.45 at wavelengths from 400 nm to 410 nm, whereas the compounds of the present invention had extinction coefficients from 0.53 to 1.08. This indicates that the compound of the present invention absorbs the light at wavelengths from 400 nm to 410 nm of sunlight well and the light does not affect the material inside the element.

Example 11

[0155] An absorbance of the compound of the present invention was measured at wavelengths of 400 nm and 410 nm by adjusting a concentration of the compound to 10.sup.−5 mol/L in toluene solution. After adjusting concentrations of the compound to the 4 different concentrations of 5×10.sup.−6 mo/L, 1×10.sup.−5 mo/L, 1.5×10.sup.−5 mo/L, and 2.0×10.sup.−5 mol/L in toluene solution, an absorbance coefficient was calculated from the calibration curve obtained by measuring the 4 different concentrations of the compound in toluene solution using an ultraviolet-visible near-infrared spectrometer (made by JASCO, V-650). For comparison, the comparative compounds (2-1), (2-2), (2-3), and (2-4) represented by the above structural formulae were also measured. The measurement results are summarized in Table 2.

TABLE-US-00003 TABLE 2 Peak Absor- Absor- wave- bance bance length (λ: 400 (λ: 410 Absorption (λmax) nm) nm) coefficient Exemplified Compound (1-18) 372 nm 0.76 0.28 123234 Exemplified Compound (1-6) 378 nm 1.21 0.95 138753 Exemplified Compound (1-17) 373 nm 0.79 0.27 120059 Exemplified Compound (1-5) 375 nm 1.23 1.00 130062 Exemplified Compound (1-19) 384 nm 1.02 0.38 133851 Exemplified Compound (1-7) 395 nm 1.38 1.18 139636 Exemplified Compound (1-13) 374 nm 0.74 0.58 105333 Exemplified Compound (1-1) 389 nm 1.15 0.90 119428 Comparative Compound (2-1) 305 nm 0.02 0.01 114814 Comparative Compound (2-2) 305 nm 0.02 0.00 98970 Comparative Compound (2-3) 345 nm 0.60 0.21 100841 Comparative Compound (2-4) 373 nm 0.28 0.08 88182

[0156] Absorbance of the comparative compounds at a wavelength of 400 nm is between 0.02 and 0.60, whereas that of the compounds of the present invention is between 0.74 and 1.38. The compounds of the present invention have larger values. The absorbance of the comparative compounds at a wavelength of 410 nm is between 0.00 and 0.21, whereas that of the compounds of the present invention is between 0.27 and 1.18. The compounds of the present invention have larger values. This indicates that the compound of the present invention can absorb light having a wavelength of 400 nm to 410 nm of sunlight well, and that an absorption coefficient of the compound of the present invention has a value of 100,000 or more. That is, the compound of the present invention absorbs light well under the same concentration conditions. The compound of the present invention also absorbs light with increasing thickness of the thin film, indicating that the material is excellent in light resistance.

Example 12

[0157] As shown in FIG. 6, the organic EL element was prepared by depositing a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a luminous layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9, and a capping layer 10, in this order, on a glass substrate 1 on which a reflective ITO electrode, as a metal anode 2, was previously formed.

[0158] Specifically, the glass substrate 1, on which ITO having a film thickness of 50 nm, a reflective film of silver alloy having a film thickness of 100 nm, and ITO having a film thickness of 5 nm were sequentially formed, was subjected to ultrasonic cleaning in isopropyl alcohol for 20 minutes, and then was dried for 10 minutes on a hot plate heated to 250° C. After UV ozone treatment was performed for 2 minutes, the glass substrate with ITO was attached to a vacuum vapor deposition apparatus, and then, the pressure of the vacuum vapor deposition apparatus was reduced to 0.001 Pa or less. Subsequently, as the hole injection layer 3, an electron acceptor (Acceptor-1) represented by the following structural formula and a compound (3-1) represented by the following structural formula were subjected to binary deposition at a deposition rate at which the deposition rate ratio was Acceptor-1: compound (3-1)=3:97 so as to cover the metal anode 2, thereby forming a film thickness of 10 nm. On the hole injection layer 3, the compound (3-1) represented by the following structural formula was subjected to deposition to form the first hole transport layer 4 having a film thickness of 70 nm. On the first hole transport layer 4, a compound (3-2) represented by the following structural formula was subjected to deposition to form the second hole transport layer 5 having a film thickness of 10 nm. On the second hole transport layer 5, a compound (3-3) represented by the following structural formula and a compound (3-4) represented by the following structural formula were subjected to binary deposition at a deposition rate at which the deposition rate ratio was (3-3): (3-4)=5:95 to form the luminous layer 6 having a film thickness of 40 nm. On the luminous layer 6, a compound (3-5) represented by the following structural formula and a compound (3-6) represented by the following structural formula were subjected to binary deposition at a deposition rate at which the deposition rate ratio was (3-5): (3-6)=50:50 to form the electron transport layer 7 having a film thickness of 30 nm. On the electron transport layer 7, lithium fluoride was subjected to deposition to form the electron injection layer 8 having a film thickness of 1 nm.

[0159] On the electron injection layer 8, a magnesium silver alloy was subjected to deposition to form the cathode 9 having a film thickness of 12 nm. Finally, the compound (1-18) of Example 1 was subjected to deposition to form the capping layer 10 having a film thickness of 60 nm. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature.

[0160] The measurement results of emission characteristics by applying DC voltage to the fabricated organic EL element are summarized in Table 3.

##STR00014## ##STR00015## ##STR00016##

Example 13

[0161] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-6) of Example 2 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00017##

Example 14

[0162] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-17) of Example 3 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00018##

Example 15

[0163] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-5) of Example 4 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00019##

Example 16

[0164] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-19) of Example 5 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00020##

Example 17

[0165] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-7) of Example 6 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00021##

Example 18

[0166] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-13) of Example 7 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00022##

Example 19

[0167] An organic EL element was produced under the same conditions as in Example 12, except that the compound (1-1) of Example 8 was used instead of the compound (1-18) of Example 1 as the material of the capping layer 10. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics when a DC voltage was applied to the fabricated organic EL element are summarized in Table 3.

##STR00023##

Comparative Example 1

[0168] For comparison, an organic EL element was prepared under the same conditions as in Example 7, except that a comparative compound (2-1) represented by the following structural formula was used instead of the compound (1-18) of Example 1 to form the capping layer 10 having a film thickness of 60 nm. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics by applying DC voltage to the fabricated organic EL element are summarized in Table 3.

##STR00024##

Comparative Example 2

[0169] For comparison, an organic EL element was prepared under the same conditions as in Example 7, except that a comparative compound (2-2) represented by the following structural formula was used instead of the compound (1-18) of Example 1 to form the capping layer 10 having a film thickness of 60 nm. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics by applying DC voltage to the fabricated organic EL element are summarized in Table 3.

##STR00025##

Comparative Example 3

[0170] For comparison, an organic EL element was prepared under the same conditions as in Example 7, except that a comparative compound (2-3) of the following structural formula was used instead of the compound (1-18) of Example 1 to form the capping layer 10 having a film thickness of 60 nm. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics by applying DC voltage to the fabricated organic EL element are summarized in Table 3.

##STR00026##

Comparative Example 4

[0171] For comparison, an organic EL element was prepared under the same conditions as in Example 7, except that a comparative compound (2-4) represented by the following structural formula was used instead of the compound (1-18) of Example 1 to form the capping layer 10 having a film thickness of 60 nm. The characteristics of the fabricated organic EL element were measured in the atmosphere at room temperature. The measurement results of emission characteristics by applying DC voltage to the fabricated organic EL element are summarized in Table 3.

##STR00027##

[0172] Element lifetimes of organic EL elements prepared in Examples 12 to 19 and Comparative Examples 1 to 4 were measured, and the results are summarized in Table 3. The element lifetime was measured as the time until the luminance decayed to 95% of an initial luminance which was set to 100%, when the element was driven at a constant current of 10 mA/cm.sup.2.

TABLE-US-00004 TABLE 3 Luminous Power Voltage Luminance efficiency efficiency Element [V] [cd/m.sup.2] [cd/A] [lm/W] lifetime Capping layer (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) 95% decay Example 12 Exemplified Compound (1-18) 4.06 16671 166.89 129.33 365 hrs Example 13 Exemplified Compound (1-6) 4.01 17154 171.58 134.48 386 hrs Example 14 Exemplified Compound (1-17) 4.04 16321 163.22 126.95 377 hrs Example 15 Exemplified Compound (1-5) 4.04 16559 165.75 128.95 368 hrs Example 16 Exemplified Compound (1-19) 4.03 16510 165.21 128.97 389 hrs Example 17 Exemplified Compound (1-7) 4.02 16770 167.79 131.18 369 hrs Example 18 Exemplified Compound (1-13) 4.07 16419 164.37 126.91 382 hrs Example 19 Exemplified Compound (1-1) 4.03 16997 170.09 132.59 384 hrs Comparative Example 1 Comparative Compound (2-1) 4.02 13139 131.45 102.78 291 hrs Comparative Example 2 Comparative Compound (2-2) 4.01 14625 146.30 114.55 302 hrs Comparative Example 3 Comparative Compound (2-3) 4.06 13814 138.29 107.02 301 hrs Comparative Example 4 Comparative Compound (2-4) 4.03 13022 130.31 101.68 257 hrs

[0173] As shown in Table 3, the drive voltages at a current density of 10 mA/cm.sup.2 are almost the same between the elements of Comparative Examples 1 to 4 using the comparative compound and the elements of Examples 12 to 19 of the present invention; however, luminance, luminous efficiency, power efficiency, and lifetime of the elements of Examples 12 to 19 of the present embodiment were significantly improved compared with those of the elements of Comparative Examples 1 to 4 using the comparative compound. This indicates that light extraction efficiency can be greatly improved by including, in the capping layer, a material having a high refractive index and suitably used for the organic EL element of the present embodiment.

INDUSTRIAL APPLICABILITY

[0174] As described above, the amine compound represented by general formula (1), which is suitably used in the organic EL element of the present invention, has a high absorption coefficient, has a high refractive index, can greatly improve the light extraction efficiency, and has a stable thin film state. Therefore, the amine compound is excellent as a compound for the organic EL element. By manufacturing an organic EL element using the compound, not only can high efficiency be obtained, but durability and light resistance can also be improved because the light of sunlight is absorbed and the material inside the element is not affected. Further, by using the compound having no absorption in each of the wavelength regions of blue, green, and red, the compound is particularly suitable for displaying a clear and bright image with good color purity. For example, the compound can be applied to home appliances and lighting.

REFERENCE NUMBERS IN DRAWINGS

[0175] 1 Glass substrate [0176] 2. Metal anode [0177] 3. Hole injection layer [0178] 4. First hole transport layer [0179] 5. Second hole transport layer [0180] 6. Luminous layer [0181] 7. Electron transport layer [0182] 8. Electron injection layer [0183] 9. Cathode [0184] 10 Capping layer