JP2012188416A - Novel 2,7-bisanthrylnaphthalene compound and organic electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element excellent in low voltage and element life.SOLUTION: The organic electroluminescent element is produced by using a 2,7-bisanthrylnaphthalene compound, which is obtained by substituting the 2-position and 7-position of naphthalene with specific anthracene derivatives, as a light emitting layer material.

Description

  The present invention relates to a novel 2,7-bisanthrylnaphthalene compound, a material for a light emitting layer containing the compound, and an organic electroluminescent element (hereinafter referred to as an organic EL element or simply referred to as a lighting device or a display device such as a color display). It may be abbreviated as an element.). More specifically, the present invention relates to an organic electroluminescent device that has improved driving voltage, lifetime, and the like by using a novel 2,7-bisanthrylnaphthalene compound in a light emitting layer.

  The organic EL element is a self-luminous light emitting element, and is expected as a light emitting element for display or illumination, and has been actively researched in recent years. In order to promote the practical use of organic EL elements, it is indispensable to reduce the power consumption and extend the life of the elements, and particularly, it is a serious problem with respect to blue light emitting elements.

  Therefore, various studies have been made on organic light-emitting materials, and improvements have been made on styrylamine, anthracene derivatives, and the like with the aim of improving the luminous efficiency and lifetime of blue light-emitting elements (for example, Non-Patent Document 1, Patent Documents 1 and 2). Furthermore, the development of materials for displays has been promoted, and a material having a structure capable of obtaining blue light emission with a higher color purity (short emission spectrum wavelength and narrow half-value width) has been required to improve the NTSC ratio. Yes.

  So far, there are reports on anthracene derivatives as materials for light emitting layers of blue elements (the following patent documents 1 to 5 and the following non-patent documents 1 to 5). When the light emitting layer is formed using the material, it is difficult to improve the life characteristics of the organic EL element with high luminous efficiency.

JP 2005-139390 A JP 2004-6222 A International Publication No. 01/21729 Pamphlet Japanese Patent Laid-Open No. 2001-284050 Special Publication 2009-518342

Materials Science and Engineering: R: Reports Volume 39, Issues 5-6, Pages 143-222, 2002. Appl. Phys. Lett. 91, 251111 (2007) Appl. Phys. Lett. 89, 252903 (2006) Appl. Phys. Lett. 90, 123506 (2007) Appl. Phys. Lett. 91, 083515 (2007)

  Under the circumstances as described above, development of a high color purity blue light emitting element improved in driving voltage, element lifetime, and the like, and a display device using the blue light emitting element are desired.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed novel 2,7-bisanthrylnaphthalene compounds represented by the general formula (1) and used them as a light emitting layer of a blue light emitting device. It has been found that an organic electroluminescence device having improved driving voltage, device life, etc. can be obtained by using it as a material for the light emitting layer to be used, and the present invention has been completed.

  That is, the present invention provides the following novel 2,7-bisanthrylnaphthalene compound, light emitting layer material, organic electroluminescent element, and a display device and an illuminating device including the organic electroluminescent element.

式（１）中、
Ａｒ^１およびＡｒ^２は、それぞれ独立して、置換されていてもよいアリールであり、
Ｒ^１およびＲ^２は、それぞれ独立して、炭素数１〜４のアルキルまたは炭素数３〜６のシクロアルキルであり、ｍおよびｎは、それぞれ独立して、０〜８の整数であり、そして、
式（１）で表される化合物における少なくとも１つの水素が重水素で置換されていてもよい。 [1] A 2,7-bisanthrylnaphthalene compound represented by the following general formula (1).

In formula (1),
Ar ¹ and Ar ² are each independently an optionally substituted aryl,
R ¹ and R ² are each independently alkyl having 1 to 4 carbons or cycloalkyl having 3 to 6 carbons, m and n are each independently an integer from 0 to 8, and ,
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium.

[2] Ar ¹ and Ar ² are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl, an alkyl having 1 to 12 carbons, and having 3 to 12 carbons Optionally substituted with cycloalkyl or aryl of 6 to 18 carbon atoms,
R ¹ and R ² are each independently alkyl having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4,
The 2,7-bisanthrylnaphthalene compound according to the above [1].

[3] Ar ¹ and Ar ² are each independently phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl or phenanthryl, and phenyl, 1-naphthyl or 2-naphthyl. May be replaced with
R ¹ and R ² are each independently methyl, isopropyl or t-butyl, and m and n are each independently 0 or 1,
The 2,7-bisanthrylnaphthalene compound according to [1] or [2] above.

[4] Ar ¹ and Ar ² are each independently phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl or phenanthryl, and phenyl, 1-naphthyl or 2-naphthyl. May be replaced with
m and n are 0,
The 2,7-bisanthrylnaphthalene compound according to any one of [1] to [3] above.

[5] The method according to any one of [1] to [4], which is represented by the following formula (1-1), formula (1-22), formula (1-57), or formula (1-58): 2,7-bisanthrylnaphthalene compound.

[6] A light emitting layer material containing the 2,7-bisanthrylnaphthalene compound according to any one of [1] to [5].

[7] An organic electroluminescence device comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the light emitting layer material described in [6] above.

[8] The organic electroluminescent element as described in [7] above, wherein the light emitting layer contains at least one selected from the group consisting of an amine having a stilbene structure, an aromatic amine derivative and a coumarin derivative.

[9] Furthermore, it has an electron transport layer and / or an electron injection layer arranged between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is a quinolinol-based metal complex, The organic electroluminescent device according to the above [7] or [8], comprising at least one selected from the group consisting of a pyridine derivative, a phenanthroline derivative, a borane derivative and a benzimidazole derivative.

[10] At least one of the electron transport layer and the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one selected from the group consisting of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescent element according to [9], which is contained.

[11] A display device comprising the organic electroluminescent element according to any one of [7] to [10].

[12] A lighting device comprising the organic electroluminescent element according to any one of [7] to [10].

  According to a preferred aspect of the present invention, an organic electroluminescence device having a low driving voltage and a long device life can be provided. In particular, conventional problems can be solved as a blue light-emitting element with high color purity. Furthermore, it is possible to provide a display device, a lighting device, and the like provided with this effective organic electroluminescent element.

It is a schematic sectional drawing which shows the organic electroluminescent element which concerns on this embodiment.

1. 2,7-bisanthrylnaphthalene compound represented by the general formula (1) First, the 2,7-bisanthrylnaphthalene compound represented by the general formula (1) will be described in detail. The compound of the present invention is a compound in which two anthracenes substituted with aryl or the like are bonded via naphthalene, in particular, a compound in which two anthracenes are bonded at the 2-position and 7-position of naphthalene. By selecting an appropriate bonding form, the compound achieves a superior device lifetime as a material for the light emitting layer.

As “aryl” in Ar ¹ and Ar ² of the general formula (1), aryl having 6 to 24 carbon atoms is preferable, aryl having 6 to 14 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. Ar ¹ and Ar ² may be the same or different, but are preferably the same.

  Specific examples of the “aryl” include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, and condensed bicyclic aryl (1-, 2-) naphthyl. Terphenylyl which is a tricyclic aryl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Acenaphth, which is a fused tricyclic aryl Ren- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl) which is a tetracyclic aryl -3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenyl), condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, chrysene- (1-, 2-, 3-, 4-, 5-, 6-) yl, fused pentacyclic aryl Perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-) yl, and 4- (Naphthalen-1-,-2-yl) phenyl, 3- (naphthalen-1-,-2-yl) phenyl, 4-phenylnaphthalen-1-yl, 1,1′-binaphthalene obtained by combining -4-yl, 4- (phenanthrene-9-yl) phenyl and the like.

Among them, as Ar ¹ and Ar ² , phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, chrysenyl or triphenylenyl are preferable, and phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2- Naphthyl or phenanthryl is particularly preferred.

The substituent for “aryl” in Ar ¹ and Ar ² is not particularly limited as long as a low driving voltage and an excellent device lifetime can be obtained, but preferably an alkyl having 1 to 12 carbon atoms and 3 carbon atoms. -12 cycloalkyl, C6-C18 aryl, etc. are mentioned.

  The “alkyl having 1 to 12 carbon atoms” as the substituent may be either a straight chain or a branched chain. That is, it is a linear alkyl having 1 to 12 carbons or a branched alkyl having 3 to 12 carbons. More preferably, it is C1-C6 alkyl (C3-C6 branched alkyl), More preferably, it is C1-C4 alkyl (C3-C4 branched alkyl). is there. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like are mentioned, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl is preferable. More preferably, isopropyl or t-butyl.

  Specific examples of the “cycloalkyl having 3 to 12 carbon atoms” as the substituent include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl. can give.

  Moreover, about "aryl of 6-18 carbons" as this substituent, what is comprised by 6-18 carbons from the aryl mentioned above can be cited as a specific example.

The substituent to “aryl” in Ar ¹ and Ar ² is preferably unsubstituted, but when a substituent is present, the number is, for example, the maximum number of substituents, preferably 1 to 1. Three, more preferably 1-2, and still more preferably 1.

As “alkyl having 1 to 4 carbon atoms” and “cycloalkyl having 3 to 6 carbon atoms” in R ¹ and R ² of the general formula (1), the description of alkyl and cycloalkyl as the substituents of the aryl described above can be given. Can be quoted. R ¹ and R ² may be the same or different, but are preferably the same. M and n are integers of 0 to 8, but are preferably integers of 0 to 4, more preferably 0 or 1, and even more preferably 0. m and n may be the same or different, but are preferably the same.

Further, all or a part of the hydrogen atoms in Na ¹ , Ar ² , R ^1, or R ² constituting the compound represented by the general formula (1) and substituted with anthracene in deuterium are deuterium. There may be.

  Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-158). Among these, preferred compounds are those represented by formula (1-1) to formula (1-4), formula (1-7), formula (1-8), formula (1-10), formula (1-11), formula (1-13), Formula (1-14), Formula (1-22), Formula (1-23), Formula (1-33), Formula (1-43), Formula (1-47) to Formula ( 1-54), Formula (1-57) to Formula (1-59), Formula (1-69), Formula (1-70), Formula (1-72), Formula (1-78) to Formula (1) -84), a formula (1-90), a formula (1-91), a compound denoted by a formula (1-111)-a formula (1-113). More preferable compounds are the formula (1-1) to the formula (1-4), the formula (1-7), the formula (1-8), the formula (1-10), the formula (1-11), the formula (1). -13), Formula (1-22), Formula (1-33), Formula (1-43), Formula (1-47) to Formula (1-51), Formula (1-57) to Formula (1- 59), Formula (1-69), Formula (1-70), Formula (1-78), Formula (1-79), Formula (1-81), Formula (1-83), Formula (1-90) ), Formula (1-91), and Formula (1-111) to Formula (1-113). Further preferred compounds are those represented by formula (1-1) to formula (1-4), formula (1-13), formula (1-22), formula (1-33), formula (1-43), formula (1). -47) to formula (1-50), formula (1-57) to formula (1-59), formula (1-69), formula (1-70), formula (1-78), formula (1- 79), Formula (1-90), Formula (1-91), Formula (1-111) to Formula (1-113).

2. Method for producing 2,7-bisanthrylnaphthalene compound represented by formula (1) The 2,7-bisanthrylnaphthalene compound represented by formula (1) should be produced using a known synthesis method. Can do. For example, when the 2,7-bisanthrylnaphthalene compound represented by the formula (1) is a symmetric system (when the structures of the two anthracene derivatives are the same), the following reactions (A-1) to (A- It can be synthesized according to the route shown in 2). In addition, when the 2,7-bisanthrylnaphthalene compound represented by the formula (1) is an asymmetric system, the compound should also be synthesized according to the routes shown in the following reactions (B-1) to (B-5). You can also.

  First, the routes shown in reactions (A-1) to (A-2) will be described. First, in the reaction (A-1), naphthalene-2,7-diylbis (trifluoromethanesulfonate) is reacted by reacting naphthalene-2,7-diol with trifluoromethanesulfonic anhydride in the presence of a base. Can be synthesized.

Next, in the reaction (A-2), using a palladium catalyst, in the presence of a base, 2 equivalents of an arylanthraceneboronic acid derivative to naphthalene-2,7-diyl bis (trifluoromethanesulfonate) are subjected to a Suzuki coupling reaction. By doing so, a 2,7-bisanthrylnaphthalene compound represented by the formula (1) of the present invention can be synthesized. In the arylanthraceneboronic acid derivative, the substituent (R ¹ ), the number of substituents (m), and the substituent (Ar ¹ ) are the same as R ¹ , m, and Ar ¹ in the formula (1). Ar ¹ = Ar ² , R ¹ = R ² , m = n. Further, the boronic acid ester can be used in place of the arylanthracene boronic acid derivative.

  In addition, in the Suzuki coupling reaction in the reaction (A-2), the reactive groups in the two compounds to be reacted are interchanged, so that trifluoromethane of naphthalene-2,7-diylbis (boronic acid or boronic ester) and arylanthracene derivative is obtained. It can also be reacted with lomethanesulfonate. Furthermore, Negishi coupling can be used instead of Suzuki coupling. In this case, a zinc chloride complex is used instead of a compound having boronic acid or boronic acid ester. In the case of this Negishi coupling, the reaction can be carried out even if the reactive groups are alternately replaced in the same manner as described above.

  Next, the route shown in the reactions (B-1) to (B-5) will be described. First, in the reaction (B-1), 7-methoxynaphthalen-2-yl trifluoromethanesulfonate is synthesized by reacting trifluoromethanesulfonic anhydride with 7-methoxy-2-naphthol in the presence of a base. be able to.

Next, in the reaction (B-2), an arylanthraceneboronic acid derivative is subjected to Suzuki coupling reaction with 7-methoxynaphthalen-2-yl trifluoromethanesulfonate in the presence of a base using a palladium catalyst. A-(7-methoxynaphthalen-2-yl) -10-arylanthracene derivative can be synthesized. In addition, the substituent (R ¹ ), the number of substituents (m), and the substituent (Ar ¹ ) in the arylanthraceneboronic acid derivative are the same as R ¹ , m and Ar ¹ in the formula (1). Further, the boronic acid ester can be used in place of the arylanthracene boronic acid derivative.

  In the same manner as described in the reaction (A-2), in the reaction (B-2), the reactive group may be replaced, or Negishi coupling using a zinc chloride complex may be used instead of the Suzuki coupling. it can.

  Next, in the reaction (B-3), 7- (10-arylanthracen-9-yl) is obtained by reacting 9- (7-methoxynaphthalen-2-yl) -10-arylanthracene derivative with pyridine hydrochloride. ) -2-Naphthol derivatives can be synthesized.

  Furthermore, in the reaction (B-4), 7- (10-arylanthracen-9-yl) -2-naphthol derivative is reacted with trifluoromethanesulfonic anhydride in the presence of a base to give 7- (10- Arylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate derivatives can be synthesized.

Finally, in the reaction (B-5), an arylanthraceneboronic acid derivative is converted into a 7- (10-arylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate derivative in the presence of a base using a palladium catalyst. 2,7-bisanthrylnaphthalene compound represented by the formula (1) of the present invention can be synthesized. In addition, the substituent (R ² ), the number of substituents (n), and the substituent (Ar ² ) in the arylanthraceneboronic acid derivative are the same as R ² , n, and Ar ² in the formula (1). Further, the boronic acid ester can be used in place of the arylanthracene boronic acid derivative.

  In the same manner as described in the reaction (A-2), in the reaction (B-5), the reactive group may be replaced, or Negishi coupling using a zinc chloride complex may be used instead of the Suzuki coupling. it can.

When a palladium catalyst is used in the reaction (A-2), reaction (B-2) and reaction (B-5) described above, for example, Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd ( OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), [1.1′-bis (diphenylphosphino) ferrocene] palladium (II) dichlorito A dichloromethane complex (1: 1) or the like can be used.

  In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N- Dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1′-bis (di-t-butylphosphino) Examples include ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, and the like. .

  Examples of the base used together with the palladium catalyst include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, Examples include potassium acetate, tripotassium phosphate, and potassium fluoride.

  Furthermore, examples of the solvent used in the above reaction (A-2), reaction (B-2), and reaction (B-5) include benzene, toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, and diethyl ether. , T-butyl methyl ether, 1,4-dioxane, methanol, ethanol, isopropyl alcohol, cyclopentyl methyl ether and the like. These solvents may be used alone or as a mixed solvent. The reaction is usually carried out in the temperature range of 50 to 180 ° C, more preferably 70 to 130 ° C.

  Moreover, when using a base in reaction (A-1), reaction (B-1), and reaction (B-4), for example, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, water Potassium oxide, barium hydroxide, sodium acetate, potassium acetate, tripotassium phosphate, potassium fluoride, cesium fluoride, trimethylamine, triethylamine, pyridine and the like can be used.

Examples of the solvent used in the reaction (A-1), the reaction (B-1) and the reaction (B-4) include pyridine, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide. , CH ₂ Cl ₂ , CHCl ₃ CH ₃ CN, and the like. These solvents may be used alone or as a mixed solvent. The reaction is usually carried out in the temperature range of -10 to 50 ° C, more preferably 0 to 30 ° C.

  Examples of the reaction solvent used in the reaction (B-3) include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, and quinoline. A solvent may be used independently and may be used as a mixed solvent. In some cases, no solvent may be used. The reaction is usually carried out in the temperature range of 150 to 220 ° C, more preferably 170 to 200 ° C.

  In addition, the compounds of the present invention include those in which at least a part of the hydrogen atoms are substituted with deuterium. Such a compound can be obtained by using a raw material in which a desired position is deuterated. It can be synthesized in the same way.

3. Organic Electroluminescent Device The 2,7-bisanthrylnaphthalene compound according to the present invention can be used, for example, as a material for an organic electroluminescent device. Below, the organic electroluminescent element which concerns on this embodiment is demonstrated in detail based on drawing. FIG. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to this embodiment.

<Structure of organic electroluminescence device>
An organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. A hole transport layer 104 provided on the light emitting layer 105, a light emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light emitting layer 105, and an electron transport layer 106. And the cathode 108 provided on the electron injection layer 107.

  The organic electroluminescent element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer. An electron transport layer 106 provided on 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, and a hole transport layer 104 A structure including the hole injection layer 103 provided above and the anode 102 provided on the hole injection layer 103 may be employed.

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

  As an aspect of the layer constituting the organic electroluminescence device, in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, "Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ”,“ substrate ” / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / “Electron transport layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport” Layer / cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "may be configured aspect of the" substrate / anode / light emitting layer / electron injection layer / cathode ".

<Substrate in organic electroluminescence device>
The substrate 101 serves as a support for the organic electroluminescent device 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescence device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

  Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide). Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances currently used as an anode of an organic electroluminescent element, and can use it.

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode. However, since it is now possible to supply a substrate of about 10Ω / □, for example, 100-5Ω / □, preferably 50-5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescence device>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

  As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

  As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a charge transport material for holes, a p-type semiconductor, and a hole injection of an organic electroluminescent element are used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino group in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl- , 1′-diamine, 4,4 ′, 4 ″ -tris (3-methylphenyl (phenyl) amino) triphenylamine and other triphenylamine derivatives, starburstamine derivatives, etc., stilbene derivatives, phthalocyanine derivatives (metal-free) , Copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate having the above monomers in the side chain And styrene derivatives, polyvinyl carbazole, and polysilane are preferable, but the compound is not particularly limited as long as it is a compound that can form a thin film necessary for manufacturing a light-emitting element, inject holes from the anode, and further transport holes. Absent.

  It is also known that the conductivity of organic semiconductors is strongly influenced by the doping. Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials. (For example, the document “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998)”) and the document “J. Blochwitz, M Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. Known matrix substances having hole transporting properties include, for example, benzidine derivatives (TPD and the like), starburst amine derivatives (TDATA and the like), and specific metal phthalocyanines (particularly zinc phthalocyanine ZnPc and the like). 2005-167175).

<Light emitting layer in organic electroluminescent element>
The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency. In the present invention, the compound represented by the above formula (1) can be used as the material for the light emitting layer.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire light emitting layer material. It is. The compound represented by the above formula (1) according to the present invention is particularly preferably a host material.

  The amount of dopant material used depends on the type of dopant material, and may be determined according to the characteristics of the dopant material. The standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.

  Host materials that can be used in combination with the compound represented by the above formula (1) according to the present invention include fused ring derivatives such as anthracene and pyrene, bisstyrylanthracene derivatives and distyryl, which have been known as light emitters. Examples thereof include bisstyryl derivatives such as benzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, and benzofluorene derivatives.

  Moreover, it does not specifically limit as dopant material, A known compound can be used and it can select from various materials according to a desired luminescent color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, benzthiazole derivatives, benzimidazole derivatives, benztriazole derivatives, oxazoles Derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, distyrylbenzene derivatives, etc. (JP-A-1-245087), bisstyrylarylene derivatives (JP-A-2-24727) Gazette), diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, etc. Isobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzthiazolylcoumarin derivatives, 3 -Coumarin derivatives such as benzimidazolyl coumarin derivatives and 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, Nin derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1, Examples include 2,5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

  Illustrated for each color light, blue to blue-green dopant materials include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene and other aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, Aromatic heterocycles such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles, thiadiazos Azole derivatives such as sulfazole, carbazole, oxazole, oxadiazole, triazole and metal complexes thereof and N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1 Examples include aromatic amine derivatives represented by '-diamine.

  Examples of green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene, and the above blue A compound in which a substituent capable of increasing the wavelength such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group is introduced into the compound exemplified as the blue-green dopant material is also a suitable example.

  Further, examples of the orange to red dopant material include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazones Conductors and thiadiazolopyrene derivatives, etc., and longer wavelengths such as aryl groups, heteroaryl groups, arylvinyl groups, amino groups, and cyano groups can be added to the compounds exemplified above as blue to blue-green and green to yellow dopant materials. A compound into which a substituent is introduced is also a suitable example.

  In addition, as a dopant, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up.

  Among the dopant materials described above, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives are particularly preferable.

当該式中、Ａｒ^１は炭素数６〜３０のアリールに由来するｍ価の基であり、Ａｒ^２およびＡｒ^３は、それぞれ独立して炭素数６〜３０のアリールであるが、Ａｒ^１〜Ａｒ^３の少なくとも１つはスチルベン構造を有し、Ａｒ^１〜Ａｒ^３は置換されていてもよく、そして、ｍは１〜４の整数である。 The amine having a stilbene structure is represented by the following formula, for example.

In the formula, Ar ¹ is an m-valent group derived from aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, Ar ^{1 to} Ar ^At least one of ³ has a stilbene structure, Ar ^{1 to} Ar ³ may be substituted, and m is an integer of 1 to 4.

当該式中、Ａｒ^２およびＡｒ^３は、それぞれ独立して炭素数６〜３０のアリールであり、Ａｒ^２およびＡｒ^３は置換されていてもよい。 The amine having a stilbene structure is more preferably a diaminostilbene represented by the following formula.

In the formula, Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, stilbene, distyrylbenzene, distyrylbiphenyl, and distyryl. Examples include fluorene.

Specific examples of amines having a stilbene structure include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl) ) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (2-naphthyl) -4,4′-diaminostilbene, N, N′-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) styryl] -biphenyl, 1,4-bis [4′-bis (diphenylamino) styryl] -benzene, 2,7-bis [4′-bis (diphenylamino) styryl] -9,9-dimethyl Fluorene, 4,4′-bis (9-ethyl-3-cal And bazovinylene) -biphenyl and 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl.
Moreover, you may use the amine which has a stilbene structure described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc.

Examples of perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene 3- (9′-anthryl) -8,11-di (t-butyl) perylene, 3,3′-bis (8,11-di (t-butyl) perylenyl), and the like.
JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A No. 2000-34234, JP-A No. 2001-267075, JP-A No. 2001-217077 and the like may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimesitylboryl) anthracene, 9-phenyl-10- (dimesitylboryl) anthracene, 4- (9′-anthryl) dimesitylborylnaphthalene, 4- (10 ′). -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) -10- (Dimesitylboryl) anthracene and the like.
Moreover, you may use the borane derivative described in the international publication 2000/40586 pamphlet.

当該式中、Ａｒ^４は炭素数６〜３０のアリールに由来するｎ価の基であり、Ａｒ^５およびＡｒ^６はそれぞれ独立して炭素数６〜３０のアリールであり、Ａｒ^４〜Ａｒ^６は置換されていてもよく、そして、ｎは１〜４の整数である。 The aromatic amine derivative is represented by the following formula, for example.

In the formula, Ar ⁴ is an n-valent group derived from aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ are It may be substituted and n is an integer from 1 to 4.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene or pyrene, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ are substituted. An aromatic amine derivative in which n is 2 and n is 2 is more preferable.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorenephenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, and pentacene.

  Examples of the aromatic amine derivative include chrysene-based compounds such as N, N, N ′, N′-tetraphenylchrysene-6,12-diamine, N, N, N ′, N′-tetra (p-tolyl). Chrysene-6,12-diamine, N, N, N ′, N′-tetra (m-tolyl) chrysene-6,12-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) chrysene -6,12-diamine, N, N, N ', N'-tetra (naphthalen-2-yl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis ( 4-ethylphenyl) chrysene-6 2-diamine, N, N′-diphenyl-N, N′-bis (4-isopropylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-t-butyl) Phenyl) chrysene-6,12-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) chrysene-6,12-diamine, and the like.

  Examples of the pyrene-based compound include N, N, N ′, N′-tetraphenylpyrene-1,6-diamine, N, N, N ′, N′-tetra (p-tolyl) pyrene-1,6. -Diamine, N, N, N ', N'-tetra (m-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) pyrene-1 , 6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) ) Pyrene-1,6-diamine, N, N'-diphenyl-N, N'- Su (4-isopropylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-t-butylphenyl) pyrene-1,6-diamine, N, N′-bis (4-Isopropylphenyl) -N, N′-di (p-tolyl) pyrene-1,6-diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) -3,8- And diphenylpyrene-1,6-diamine.

  Examples of the anthracene system include N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N ′, N′-tetra (p-tolyl) anthracene-9,10-diamine. N, N, N ′, N′-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthrace -9,10-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4- t-butylphenyl) anthracene-9,10-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-di -T-butyl-N, N, N ', N'-tetra (p-tolyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-diphenyl-N, N' -Bis (4-isopropylphenyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) Anthracene-9,10-diamy 2,6-dicyclohexyl-N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N′- Bis (4-isopropylphenyl) -N, N′-bis (4-t-butylphenyl) anthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, 9,10-bis (4-Di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p- Tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino- And 9- (6-diphenylamino-2-naphthyl) anthracene.

Examples of pyrene-based compounds include N, N, N, N-tetraphenyl-1,8-pyrene-1,6-diamine and N-biphenyl-4-yl-N-biphenyl-1,8-pyrene-1. , ^6-diamine, N 1, ^{N 6} - diphenyl ^-N 1, ^{N 6} - bis - (4-trimethylsilanyl - phenyl)-1H, such 8H- 1,6-diamine.

Other examples include [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) naphthalen-2-yl] -diphenylamine, 4,4 ′. -Bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4'-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] ] -P-terphenyl, 4,4 "-bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, and the like.
Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Moreover, you may use the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, and Unexamined-Japanese-Patent No. 6-298758.

また、特開2005-126399号公報、特開2005-097283号公報、特開2002-234892号公報、特開2001-220577号公報、特開2001-081090号公報、および特開2001-052869号公報などに記載されたピラン誘導体を用いてもよい。 Examples of the pyran derivative include the following DCM and DCJTB.

Also, JP 2005-126399, JP 2005-097283, JP 2002-234892, JP 2001-220577, JP 2001-081090, and JP 2001-052869. Alternatively, pyran derivatives described in the above may be used.

<Electron injection layer and electron transport layer in organic electroluminescence device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.

  The electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, a compound conventionally used as an electron transport compound in a photoconductive material, an electron injection layer and an electron transport layer of an organic electroluminescent element can be used. It can be arbitrarily selected from known compounds used.

  Materials used for the electron transport layer or the electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, and pyrrole derivatives. And at least one selected from the condensed ring derivatives thereof and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.

  Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazoles. Derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- Triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phen Lene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2′-bis (benzo [h] quinolin-2-yl) -9,9′-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benz Imidazole derivatives (such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzthiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 '-(2,2': 6'2 "-terpyridinyl)) benzene), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), aldazine Derivatives, carbazole derivatives, India Le derivatives, phosphorus oxide derivatives, such as bis-styryl derivatives.

  In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

  Although the above-mentioned materials are used alone, they may be mixed with different materials.

  Among the materials described above, quinolinol-based metal complexes, bipyridine derivatives, phenanthroline derivatives, or borane derivatives are preferable.

式中、Ｒ^１〜Ｒ^６は水素または置換基であり、ＭはＬｉ、Ａｌ、Ｇａ、ＢｅまたはＺｎであり、ｎは１〜３の整数である。 The quinolinol-based metal complex is a compound represented by the following general formula (E-1).

In the formula, R ^{1 to} R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be, or Zn, and n is an integer of 1 to 3.

  Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3 , 4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4-me Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8- Quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl) -8-quinolinolate) (3,5-di-tert-butyl) Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-Methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bis ( 2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) ) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenol) Lat) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2 -Methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl) -8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8) Quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano- 8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis ( 2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium and the like.

式中、Ｇは単なる結合手またはｎ価の連結基を表し、ｎは２〜８の整数である。また、ピリジン−ピリジンまたはピリジン−Ｇの結合に用いられない炭素原子は置換されていてもよい。 A bipyridine derivative is a compound represented by the following general formula (E-2).

In the formula, G represents a simple bond or an n-valent linking group, and n is an integer of 2 to 8. Carbon atoms that are not used for bonding of pyridine-pyridine or pyridine-G may be substituted.

Examples of G in the general formula (E-2) include the following structural formulas. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

  Specific examples of the pyridine derivative include 2,5-bis (2,2′-bipyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Bipyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-bipyridin-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-bipyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilole, 9,10-di (2,2′-bipyridine-6) -Yl) anthracene, 9,10-di (2,2'-bipyridin-5-yl) anthracene, 9,10-di (2,3'-bipyridin-6-yl) anthracene, 9,10-di (2 , 3′-bipyridin-5-yl) anthracene, 9,10-di (2, '-Bipyridin-6-yl) -2-phenylanthracene, 9,10-di (2,3'-bipyridin-5-yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridine) 6-yl) -2-phenylanthracene, 9,10-di (2,2′-bipyridin-5-yl) -2-phenylanthracene, 9,10-di (2,4′-bipyridin-6-yl) 2-phenylanthracene, 9,10-di (2,4′-bipyridin-5-yl) -2-phenylanthracene, 9,10-di (3,4′-bipyridin-6-yl) -2-phenyl Anthracene, 9,10-di (3,4'-bipyridin-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2′-bipyridin-6-yl) thiophene, 3,4-dipheni -2,5-di (2,3'-bipyridin-5-yl) thiophene, 6'6 "-di (2-pyridyl) 2,2 ': 4', 4": 2 ", 2" '-qua Examples include terpyridine.

式中、Ｒ^１〜Ｒ^８は水素または置換基であり、隣接する基は互いに結合して縮合環を形成してもよく、Ｇは単なる結合手またはｎ価の連結基を表し、ｎは２〜８の整数である。また、一般式（Ｅ−３−２）のＧとしては、例えば、ビピリジン誘導体の欄で説明したものと同じものがあげられる。 A phenanthroline derivative is a compound represented by the following general formula (E-3-1) or (E-3-2).

In the formula, R ^{1 to} R ⁸ are hydrogen or a substituent, adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or an n-valent linking group, and n represents 2 It is an integer of ~ 8. Moreover, as G of general formula (E-3-2), the same thing as what was demonstrated in the column of the bipyridine derivative is mention | raise | lifted, for example.

  Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline- 2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9′-difluor -Bis (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and the like.

  In particular, the case where a phenanthroline derivative is used for an electron transport layer and an electron injection layer will be described. In order to obtain stable light emission over a long period of time, a material excellent in thermal stability and thin film formation is desired, and among phenanthroline derivatives, the substituent itself has a three-dimensional structure, or a phenanthroline skeleton or Those having a three-dimensional structure by steric repulsion with an adjacent substituent or those having a plurality of phenanthroline skeletons linked to each other are preferred. Furthermore, when linking a plurality of phenanthroline skeletons, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the linking unit is more preferable.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素原子、アルキル基、置換されていてもよいアリール基、置換シリル基、置換されていてもよい窒素含有複素環基、またはシアノ基の少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル基、または置換されていてもよいアリール基であり、Ｘは、置換されていてもよいアリーレン基であり、Ｙは、置換されていてもよい炭素数１６以下のアリール基、置換ボリル基、または置換されていてもよいカルバゾール基であり、そして、ｎはそれぞれ独立して０〜３の整数である。 The borane derivative is a compound represented by the following general formula (E-4), and is disclosed in detail in JP-A-2007-27587.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X is an optionally substituted arylene group And Y is an optionally substituted aryl group having 16 or less carbon atoms, a substituted boryl group, or an optionally substituted carbazole group, and n is each independently an integer of 0 to 3 is there.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素原子、アルキル基、置換されていてもよいアリール基、置換シリル基、置換されていてもよい窒素含有複素環基、またはシアノ基の少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル基、または置換されていてもよいアリール基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子、アルキル基、置換されていてもよいアリール基、置換シリル基、置換されていてもよい窒素含有複素環基、またはシアノ基の少なくとも一つであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレン基であり、ｎはそれぞれ独立して０〜３の整数であり、そして、ｍはそれぞれ独立して０〜４の整数である。 Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-1), and further the following general formulas (E-4-1-1) to (E-4) The compound represented by -1-4) is preferable. Specific examples include 9- [4- (4-Dimesitylborylnaphthalen-1-yl) phenyl] carbazole, 9- [4- (4-Dimesitylborylnaphthalen-1-yl) naphthalen-1-yl. Carbazole and the like.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R ²¹ and R ²² are each independently , A hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group, and X ¹ is a substituted Or an arylene group having 20 or less carbon atoms, n is each independently an integer of 0 to 3, and m is each independently an integer of 0 to 4.

各式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素原子、アルキル基、置換されていてもよいアリール基、置換シリル基、置換されていてもよい窒素含有複素環基、またはシアノ基の少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル基、または置換されていてもよいアリール基であり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレン基であり、そして、ｎはそれぞれ独立して０〜３の整数である。 Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-2), and a compound represented by the following general formula (E-4-2-1) Is preferred.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X ¹ is an optionally substituted carbon. An arylene group having a number of 20 or less, and each n is independently an integer of 0 to 3.

式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In the formula, R ^{31 to} R ³⁴ are each independently any of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl or phenyl It is.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素原子、アルキル基、置換されていてもよいアリール基、置換シリル基、置換されていてもよい窒素含有複素環基、またはシアノ基の少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル基、または置換されていてもよいアリール基であり、Ｘ^１は、置換されていてもよい炭素数１０以下のアリーレン基であり、Ｙ^１は、置換されていてもよい炭素数１４以下のアリール基であり、そして、ｎはそれぞれ独立して０〜３の整数である。 Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-3-3), and further, the following general formula (E-4-3-1) or (E-4) The compound represented by -3-2) is preferable.

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X ¹ is an optionally substituted carbon. It is an arylene group having several tens or less, Y ¹ is an optionally substituted aryl group having 14 or less carbon atoms, and n is each independently an integer of 0 to 3.

各式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

式中、Ａｒ^１〜Ａｒ^３はそれぞれ独立に水素または置換されてもよい炭素数６〜３０のアリールである。特に、Ａｒ^１が置換されてもよいアントリルであるベンゾイミダゾール誘導体が好ましい。 The benzimidazole derivative is a compound represented by the following general formula (E-5).

In the formula, Ar ^{1 to} Ar ³ are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. In particular, a benzimidazole derivative which is anthryl optionally substituted with Ar ¹ is preferable.

  Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, and fluorene-1- Yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, phenalen-1-yl, phenalen-2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthen-1-yl, fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl, fluoranthen-8-yl, Triphenylene-1-yl, triphenylene-2-yl, pyreth -1-yl, pyren-2-yl, pyren-4-yl, chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, chrysene-6 -Yl, naphthacene-1-yl, naphthacene-2-yl, naphthacene-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, pentacene-1-yl, pentasen-2-yl , Pentacene-5-yl and pentacene-6-yl.

  Specific examples of the benzimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalene-2) -Yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1- Phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4- (10 -(Naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalene) 2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl ) -2-phenyl-1H-benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole is there.

  The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.

  Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

<Cathode in organic electroluminescence device>
The cathode 108 serves to inject electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

  The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as that for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum) are preferred. Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are often often unstable in the atmosphere. In order to improve this point, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium and a highly stable electrode is used. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

  Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating.

<Binder that may be used in each layer>
The materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc. is there.

<Method for producing organic electroluminescent element>
Each layer constituting the organic electroluminescent element is formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or cast method, coating method, etc. It can be formed by using a thin film. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like. Deposition conditions generally include a boat heating temperature of 50 to 400 ° C., a degree of vacuum of 10 ⁻⁶ to 10 ⁻³ Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −150 to + 300 ° C., and a film thickness of 2 nm to 5 μm. It is preferable to set appropriately within the range.

  Next, as an example of a method for producing an organic electroluminescent device, an organic electric field composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode. A method for manufacturing a light-emitting element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a desired organic electroluminescent element can be obtained. In the preparation of the above-described organic electroluminescence device, the order of preparation may be reversed, and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode may be fabricated in this order. Is possible.

  When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, the organic electroluminescent device is transparent or translucent. Luminescence can be observed from the electrode side (anode or cathode, and both). The organic electroluminescence device emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

<Application examples of organic electroluminescent devices>
The present invention can also be applied to a display device provided with an organic electroluminescent element or a lighting device provided with an organic electroluminescent element.
A display device or an illuminating device including an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

  Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

  A matrix means a pixel in which pixels for display are two-dimensionally arranged such as a lattice or a mosaic, and displays a character or an image with a set of pixels. The shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 μm or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become. In monochrome display, pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. The matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.

  In the segment system (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for liquid crystal display devices, especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness. The backlight using the light emitting element according to the embodiment is thin and lightweight.

  First, synthesis examples of the 2,7-bisanthrylnaphthalene compound used in the examples are described below.

<Synthesis Example of Compound Represented by Formula (1-1)>

<Synthesis of naphthalene-2,7-diyl bis (trifluoromethanesulfonate)>
First, under a nitrogen atmosphere, 48.1 g of naphthalene-2,7-diol and 380 ml of pyridine were placed in a flask, cooled to 0 ° C., and then 203.1 g of trifluoromethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. Next, water was added to the reaction solution, the target component was extracted with toluene, and the crude product obtained by concentrating the organic layer under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 6/1 (volume ratio). )) To obtain 112.4 g (yield: 88%) of the first intermediate compound, naphthalene-2,7-diyl bis (trifluoromethanesulfonate). The scheme is shown in “Reaction 1” below.

<Synthesis of 2,7-bis (10-phenylanthracen-9-yl) naphthalene>
Next, under a nitrogen atmosphere, naphthalene-2,7-diyl bis (trifluoromethanesulfonate) 4.24 g, (10-phenylanthracen-9-yl) boronic acid 6.26 g, tetrakis, the first intermediate compound 0.35 g of (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 8.49 g of potassium phosphate and 40 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 9/1 (volume ratio)) The flask was stirred for 5 minutes. Thereafter, 4 ml of water was added and refluxed for 3 hours. After the heating, the reaction solution was cooled, 40 ml of methanol was added, and the precipitate was filtered. The precipitate was further washed with methanol and water to obtain a crude product of the compound represented by the desired formula (1-1). The crude product was subjected to short column purification with silica gel (solvent: toluene), then washed with ethyl acetate, recrystallized with toluene, and further purified by sublimation to obtain 2,7-bis ( 2.4 g (yield: 38%) of 10-phenylanthracen-9-yl) naphthalene was obtained. The scheme is shown in “Reaction 2” below.

The structure of the objective compound (1-1) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.25 (d, 1H), 8.04 (s, 1H), 7.86 to 7.83 (m, 2H), 7.74 to 7.72 ( m, 3H), 7.64-7.49 (m, 5H), 7.39-7.34 (m, 4H).

The glass transition temperature (Tg) of the target compound (1-1) was 193 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

<Synthesis Example of Compound Represented by Formula (1-22)>

<Synthesis of 2,7-bis (10- (naphthalen-1-yl) anthracen-9-yl) naphthalene>
Under a nitrogen atmosphere, naphthalene-2,7-diyl bis (trifluoromethanesulfonate) 8.49 g, (10-naphthalen-1-yl) anthracen-9-yl) boronic acid 14.62 g as the first intermediate compound , Tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.69 g, potassium phosphate 16.98 g and a mixed solvent of toluene and ethanol 80 ml (toluene / ethanol = 4/1 (volume ratio)) ) Was placed in a flask and stirred for 5 minutes. Thereafter, 7 ml of water was added and refluxed for 3 hours. After completion of the heating, the reaction solution was cooled, 100 ml of methanol was added, and the precipitate was filtered. The precipitate was further washed with methanol and water to obtain a target crude product of the compound represented by the formula (1-22). The crude product was subjected to short column purification with silica gel (solvent: toluene), then washed with a mixed solvent of methanol and ethyl acetate (methanol / ethyl acetate = 4/1 (volume ratio)), and recrystallized with toluene. Then, further purification by sublimation was performed to obtain 8.9 g (yield: 61%) of 2,7-bis (10- (naphthalen-1-yl) anthracen-9-yl) naphthalene as the target compound. The scheme is shown in “Reaction 3” below.

The structure of the objective compound (1-22) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.28 (t, 1H), 8.17-8.10 (q, 1H), 8.08 (d, 1H), 8.02 (t, 1H) , 7.92-7.69 (m, 4H), 7.63-7.59 (m, 1H), 7.52-7.46 (m, 3H), 7.38-7.34 (m, 2H), 7.27-7.21 (m, 4H).

The glass transition temperature (Tg) of the target compound (1-22) was 240 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

<Synthesis Example of Compound Represented by Formula (1-57)>

<Synthesis of 7-methoxynaphthalen-2-yl trifluoromethanesulfonate>
First, in a nitrogen atmosphere, 75 g of 7-methoxy-2-naphthol and 200 ml of pyridine were placed in a flask, cooled to 0 ° C., and then 146 g of trifluoromethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. Next, water was added to the reaction solution, and the target component was extracted with toluene. Further, the crude product obtained by concentrating the organic layer under reduced pressure was subjected to short column purification with silica gel (solvent: toluene), and further purified by distillation under reduced pressure to obtain a second intermediate compound, 7-methoxynaphthalene- 105 g (yield: 88%) of 2-yl trifluoromethanesulfonate was obtained. The scheme is shown in “Reaction 4” below.

<Synthesis of 9- (7-methoxynaphthalen-2-yl) -10-phenylanthracene>
Next, under a nitrogen atmosphere, 91.8 g of 7-methoxynaphthalen-2-yl trifluoromethanesulfonate, 89.4 g of (10-phenylanthracen-9-yl) boronic acid, tetrakis (tri Phenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 10.4 g, potassium phosphate 127.2 g, and 600 ml (1,2,4) of a mixed solvent of 1,2,4-trimethylbenzene and t-butyl alcohol -Trimethylbenzene / t-butyl alcohol = 5/1 (volume ratio)) was placed in a flask and stirred for 5 minutes. Thereafter, 20 ml of water was added and refluxed for 5 hours. After the heating, the reaction solution was cooled, 200 ml of methanol was added, and the precipitate was filtered. The precipitate was further washed with methanol and water, and the obtained crude product was subjected to short column purification with silica gel (solvent: toluene), then washed with methanol, and the third intermediate compound 9- (7- 66 g (yield: 53%) of methoxynaphthalen-2-yl) -10-phenylanthracene was obtained. The scheme is shown in “Reaction 5” below.

<Synthesis of 7- (10-phenylanthracen-9-yl) -2-naphthol>
Next, under a nitrogen atmosphere, 66 g of the third intermediate compound 9- (7-methoxynaphthalen-2-yl) -10-phenylanthracene, 93 g of pyridine hydrochloride, and 120 ml of 1-methyl-2-pyrrolidone are placed in a flask. Heated at 175 ° C. for 3 hours. After completion of the heating, the reaction solution was cooled, 250 ml of water was added, and the precipitate was filtered. The precipitate was further washed with water and methanol, and the obtained crude product was subjected to short column purification with silica gel (solvent: toluene), and then washed with ethyl acetate to produce the fourth intermediate compound 7- (10 54 g (yield: 85%) of -phenylanthracen-9-yl) -2-naphthol were obtained. The scheme is shown in “Reaction 6” below.

<Synthesis of 7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate>
Next, under nitrogen atmosphere, 37.8 g of 7- (10-phenylanthracen-9-yl) -2-naphthol, which is the fourth intermediate compound, and 300 ml of pyridine were placed in a flask and cooled to 0 ° C. 31 g of romethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. Next, water was added to the reaction solution, and the precipitate was filtered. The precipitate was further washed with water and methanol, and the obtained crude product was subjected to short column purification with silica gel (solvent: toluene), and then washed with methanol to give the fifth intermediate compound 7- (10- 48.5 g (yield: 96%) of phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate were obtained. The scheme is shown in “Reaction 7” below.

<Synthesis of 9- (naphthalen-1-yl) -10- (7- (10-phenylanthracen-9-yl) naphthalen-2-yl) anthracene>
Finally, under a nitrogen atmosphere, the fifth intermediate compound 7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate 5.28 g, (10-naphthalen-1-yl) anthracene -9-yl) boronic acid 3.83 g, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.23 g, potassium phosphate 5.51 g and a mixed solvent of toluene and ethanol 40 ml (toluene) / Ethanol = 9/1 (volume ratio)) was placed in a flask and stirred for 5 minutes. Thereafter, 4 ml of water was added and refluxed for 3 hours. After the heating, the reaction solution was cooled, 40 ml of methanol was added, and the precipitate was filtered. The precipitate was further washed with methanol and water to obtain a crude product of the compound represented by the target formula (1-57). The crude product was subjected to short column purification with silica gel (solvent: toluene), then washed with a mixed solvent of methanol and ethyl acetate (methanol / ethyl acetate = 4/1 (volume ratio)), and recrystallized with toluene. Further, after purification by sublimation, 4.1 g of 9- (naphthalen-1-yl) -10- (7- (10-phenylanthracen-9-yl) naphthalen-2-yl) anthracene which is the target compound ( Yield: 60%). The scheme is shown in “Reaction 8” below.

The structure of the objective compound (1-57) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.27 (t, 2H), 8.13 to 8.01 (m, 4H), 7.90 to 7.46 (m, 17H), 7.39 To 7.34 (m, 6H), 7.27 to 7.19 (m, 5H).

The glass transition temperature (Tg) of the target compound (1-57) was 218 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

<Synthesis Example of Compound Represented by Formula (1-58)>

<Synthesis of 9- (naphthalen-2-yl) -10- (7- (10-phenylanthracen-9-yl) naphthalen-2-yl) anthracene>
Under nitrogen atmosphere, the fifth intermediate compound 7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate 2.64 g, (10-naphthalen-2-yl) anthracene-9- Yl) 1.92 g of boronic acid, 0.12 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 2.13 g of potassium phosphate and 30 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 9/1 (volume ratio)) was placed in a flask and stirred for 5 minutes. Thereafter, 3 ml of water was added and refluxed for 3 hours. After completion of the heating, the reaction solution was cooled, 20 ml of water was added, and the precipitate was filtered. The precipitate was further washed with water and methanol to obtain a crude product of the compound represented by the target formula (1-58). The crude product was subjected to short column purification with silica gel (solvent: chlorobenzene), then washed with ethyl acetate, recrystallized with chlorobenzene, and further purified by sublimation to obtain the target compound 9- (naphthalene-2 -Yl) -10- (7- (10-phenylanthracen-9-yl) naphthalen-2-yl) anthracene (2.4 g, yield: 70%) was obtained. The scheme is shown in “Reaction 9” below.

The structure of the objective compound (1-58) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.26 (dd, 2H), 8.11 to 8.00 (m, 5H), 7.95 to 7.91 (m, 1H), 7.87 to 7.84 (m, 4H), 7.77-7.73 (m, 6H), 7.66-7.50 (m, 8H), 7.39-7.32 (m, 8H).

The glass transition temperature (Tg) of the target compound (1-58) was 205 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

  Hereinafter, in order to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

The organic EL elements according to Example 1 and Comparative Example 1 were prepared, and the voltage (V), EL emission wavelength (nm), and external quantum efficiency (%), which are characteristics at the time of 1000 cd / m ² emission, were measured. In addition, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more when driving at a constant current at a current density at which a luminance of 2000 cd / m ² is obtained was measured.

  Note that the quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency. The ratio of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is converted into photons purely. What is shown is the internal quantum efficiency. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element. The external quantum efficiency is lower than the internal quantum efficiency because it is continuously reflected and is not emitted outside the light emitting element.

The external quantum efficiency is measured as follows. A voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m ² to cause the element to emit light. Using a spectral radiance meter SR-2A manufactured by TOPCON, the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons in the entire wavelength region observed was integrated to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

Table 1 below shows the material configuration of each layer in the manufactured organic EL elements according to Example 1 and Comparative Example 1.

In Table 1, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “NPD” is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, “BD1” is N ⁵ , N ⁵ , N ⁹ , N ⁹ , 7, 7 , -Hexaphenyl-7H-benzo [c] fluorene-5,9-diamine, “ET1” is 9,10-di ([2,2′-bipyridin] -5-yl) anthracene, Compound (C-1) Is 9-phenyl-10- (4-phenylnaphthalen-1-yl) -anthracene, and the respective chemical structures are shown below.

<Example 1>
<Element Using Compound (1-22) as Host Material for Light-Emitting Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, the compound of the present invention (1 -22) molybdenum deposition boat with BD1, molybdenum deposition boat with BD1, molybdenum deposition boat with ET1, molybdenum deposition boat with lithium fluoride (LiF) and aluminum A tungsten evaporation boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 20 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (1-22) and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (1-22) to BD1 was approximately 95: 5. Next, the evaporation boat containing ET1 was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the vapor deposition boat containing lithium fluoride (LiF) was heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, the evaporation boat containing aluminum was heated to form a cathode by depositing aluminum at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm, thereby obtaining an organic EL element.

Using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 4.1 V, the external quantum efficiency is 3.5% (blue emission with a wavelength of about 458 nm) Met. In addition, as a result of performing a constant current driving test with a current density for obtaining a luminance of 2000 cd / m ² , the time for maintaining a luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 60 hours.

<Comparative Example 1>
<Element Using Compound (C-1) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-22), which is the host material of the light emitting layer, was changed to the compound (C-1). Using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.8 V and the external quantum efficiency was 4.0% (blue emission with a wavelength of about 456 nm). Met. In addition, as a result of performing a constant current driving test with a current density for obtaining a luminance of 2000 cd / m ² , the time for maintaining a luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 40 hours.

The above results are summarized in Table 2.

Next, organic EL elements according to Examples 2 to 6 and Comparative Examples 2 and 3 were prepared, and voltage (V), EL emission wavelength (nm), external quantum efficiency (characteristics at the time of 1000 cd / m ² emission), respectively. %), And then the time for maintaining a luminance of 80% (1600 cd / m ² ) or more when driven at a constant current at a current density at which a luminance of 2000 cd / m ² is obtained was measured.

Table 3 below shows the material configuration of each layer in the produced organic EL elements according to Examples 2 to 6 and Comparative Examples 2 and 3.

In Table 3, “HT” is N ⁴ , N ⁴ , N ^{4 ′} , N ^{4 ′} -tetra [1,1′-biphenyl] -4-yl)-[1,1′-biphenyl] -4,4 ′. - diamine, "BD2" is 7,7, - dimethyl ^-N 5, ^{N 9} - diphenyl ^-N 5, ^{N 9} - bis (4- (trimethylsilanyl) phenyl)-7H-benzo [c] fluorene -5, 9-diamine, “ET2” is 4,4 ′-((2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine, “ET3” is 2- (4- (9,10 -Di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, compound (C-2) is 9- (7-([1,1′-biphenyl) ] -2-yl) naphthalen-2-yl) -10-phenylant Sen, compound (C-3) is 9- (7-([1,1′-biphenyl] -3-yl) naphthalen-2-yl) -10-phenylanthracene, and “Liq” is 8-quinolinol lithium is there. Each chemical structure is shown below.

<Example 2>
<Element Using Compound (1-22) as Host Material for Light-Emitting Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent supporting substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, the compound of the present invention (1 -22) molybdenum vapor deposition boat, BD2 molybdenum vapor deposition boat, ET2 molybdenum vapor deposition boat, 8-quinolinol lithium (Liq) molybdenum vapor deposition boat, magnesium A molybdenum vapor deposition boat and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 20 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (1-22) and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of the compound (1-22) and BD2 was about 95: 5. Next, the evaporation boat containing ET2 was heated and evaporated to a film thickness of 25 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 2 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.47 V and the external quantum efficiency was 5.6% (blue emission with a wavelength of about 462 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 110 hours.

<Example 3>
<Element Using Compound (1-57) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-22) which is the host material of the light emitting layer was changed to the compound (1-57). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.75 V and the external quantum efficiency was 5.48% (blue emission with a wavelength of about 460 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 75 hours.

<Comparative example 2>
<Element Using Compound (C-2) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-22) which was the host material of the light emitting layer was changed to the compound (C-2). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 4.22 V, the external quantum efficiency is 5.27% (blue emission with a wavelength of about 458 nm) Met. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 52 hours.

<Example 4>
<Element Using Compound (1-1) as Host Material for Light-Emitting Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent supporting substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, the compound of the present invention (1 -1) molybdenum deposition boat with BD2, molybdenum deposition boat with BD2, molybdenum deposition boat with ET2, molybdenum deposition boat with Liq, and tungsten deposition with aluminum A boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 20 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (1-1) and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of compound (1-1) to BD2 was approximately 95: 5. Next, the evaporation boat containing ET2 and the evaporation boat containing Liq were heated at the same time to form a film having a thickness of 25 nm, thereby forming an electron transport layer. The deposition rate was adjusted so that the weight ratio of ET2 to Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 2 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, the evaporation boat containing aluminum was heated to form a cathode by depositing aluminum at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm, thereby obtaining an organic EL element.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.37 V and the external quantum efficiency was 5.64% (blue emission with a wavelength of about 457 nm). It was. In addition, as a result of performing a constant current driving test with a current density for obtaining a luminance of 2000 cd / m ² , the time for maintaining a luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 155 hours.

<Example 5>
<Element Using Compound (1-1) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by a method according to Example 4 except that the compound (ET2), which was an electron transporting material for the electron transport layer, was changed to the compound (ET3). Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.95 V and the external quantum efficiency was 5.44% (blue emission with a wavelength of about 458 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 253 hours.

<Example 6>
<Element Using Compound (1-22) as Host Material for Light-Emitting Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent supporting substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, the compound of the present invention (1 -22) molybdenum deposition boat with BD2, molybdenum deposition boat with BD2, molybdenum deposition boat with ET3, molybdenum deposition boat with Liq, and tungsten deposition with aluminum A boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 20 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (1-22) and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of the compound (1-22) and BD2 was about 95: 5. Next, the evaporation boat containing ET3 was heated and evaporated to a film thickness of 25 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 2 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, the evaporation boat containing aluminum was heated to form a cathode by depositing aluminum at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm, thereby obtaining an organic EL element.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.69 V and the external quantum efficiency was 3.67% (blue emission with a wavelength of about 458 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining a luminance of 2000 cd / m ² , the time for maintaining a luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 235 hours.

<Comparative Example 3>
<Element Using Compound (C-3) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 6 except that the compound (1-22) which was the host material of the light emitting layer was changed to the compound (C-3). Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 5.03 V and the external quantum efficiency was 4.42% (blue emission with a wavelength of about 457 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 96 hours.

The above results are summarized in Table 4.

  According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescent element having a low voltage and an excellent element lifetime, a display device including the same, a lighting device including the same.

DESCRIPTION OF SYMBOLS 100 Organic electroluminescent element 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims (12)

2,7-bisanthrylnaphthalene compound represented by the following general formula (1).

In formula (1),
Ar ¹ and Ar ² are each independently an optionally substituted aryl,
R ¹ and R ² are each independently alkyl having 1 to 4 carbons or cycloalkyl having 3 to 6 carbons, m and n are each independently an integer from 0 to 8, and ,
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium. Ar ¹ and Ar ² are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, chrysenyl, or triphenylenyl, each having 1 to 12 carbon atoms, 3 to 12 carbon atoms cycloalkyl, May be substituted with aryl having 6 to 18 carbon atoms,
R ¹ and R ² are each independently alkyl having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4,
The 2,7-bisanthrylnaphthalene compound according to claim 1. Ar ¹ and Ar ² are each independently phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl or phenanthryl, and are substituted with phenyl, 1-naphthyl or 2-naphthyl You may,
R ¹ and R ² are each independently methyl, isopropyl or t-butyl, and m and n are each independently 0 or 1,
The 2,7-bisanthrylnaphthalene compound according to claim 1 or 2. Ar ¹ and Ar ² are each independently phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl or phenanthryl, and are substituted with phenyl, 1-naphthyl or 2-naphthyl You may,
m and n are 0,
The 2,7-bisanthrylnaphthalene compound according to any one of claims 1 to 3. The 2,7-bisan according to any one of claims 1 to 4, represented by the following formula (1-1), formula (1-22), formula (1-57), or formula (1-58): Tolylnaphthalene compound.

  The material for light emitting layers containing the 2,7-bisanthryl naphthalene compound in any one of Claims 1-5.   An organic electroluminescence device comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the light emitting layer material according to claim 6.   The organic electroluminescent element according to claim 7, wherein the light emitting layer contains at least one selected from the group consisting of an amine having a stilbene structure, an aromatic amine derivative, and a coumarin derivative.   Furthermore, it has an electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer includes a quinolinol-based metal complex, a pyridine derivative, The organic electroluminescent device according to claim 7 or 8, comprising at least one selected from the group consisting of a phenanthroline derivative, a borane derivative and a benzimidazole derivative.   At least one of the electron transport layer and the electron injection layer may further include an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes, The organic electroluminescent element according to claim 9.   The display apparatus provided with the organic electroluminescent element in any one of Claims 7-10.   The illuminating device provided with the organic electroluminescent element in any one of Claims 7-10.

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