JP6041058B2 - Anthracene compound, light emitting layer material, organic electroluminescent element using the same, display device and lighting device - Google Patents

Description

  The present invention relates to an anthracene compound, a material for a light emitting layer containing the compound, and an organic electroluminescent element suitable as a display element of a display device such as a color display. More specifically, the present invention relates to an organic electroluminescent element (hereinafter, sometimes abbreviated as an organic EL element) in which the element lifetime is improved by using a specific anthracene compound in the 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.

  For this reason, various studies have been made on the material for the light emitting layer, and improvements have been made to styryl allene, anthracene derivatives, and the like with the aim of improving the device lifetime of the blue light emitting device. For example, as materials for light emitting layers of blue elements, there are reports on anthracene derivatives (Patent Documents 1 to 5 and Non-Patent Documents 1 to 5 below). In Patent Document 3, a material having naphthalene as a basic skeleton (anthracene is contained in naphthalene). In addition, Patent Document 4 discloses a compound characterized by substituting a bulky group at 6-position or 7-position of naphthyl bonded to anthracene, and Patent Document 5 binds to anthracene. A compound characterized by substituting aryl at the 7-position of naphthyl is disclosed.

JP 2005-139390 A JP 2004-6222 A JP 2010-87488 A Japanese Unexamined Patent Publication No. 2006-45503 JP 2012-104806

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, a material for a light emitting layer having an excellent device lifetime when applied to an organic EL device, in particular, a light emitting layer made of a compound having a chemical structure different from that of a conventional material in order to increase the choice of materials. Development of materials for use is desired.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in producing an anthracene compound of the general formula (1) having a specific chemical structure, and this anthracene-based material as a light-emitting layer material used for a light-emitting layer. It has been found that by using a compound, an organic EL device with improved device lifetime can be obtained, and the present invention has been completed.

  That is, the present invention provides the following anthracene compounds, light emitting layer materials, organic electroluminescent elements, and display devices and lighting apparatuses including the organic electroluminescent elements.

[1] A compound represented by the following general formula (1).
In formula (1),
R ^{1 to} R ⁵ are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted silyl;
R ^{6 to} R ⁹ are each independently hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted silyl;
Ar ^{1 to} Ar ⁵ are each independently hydrogen, optionally substituted aryl, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted silyl;
Ar ^{6 to} Ar ⁸ are each independently hydrogen, optionally substituted aryl, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted silyl;
Ar ^{9 to} Ar ¹¹ are each independently hydrogen, optionally substituted aryl, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted silyl; And
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium.

[2] R ^{1 to} R ⁵ are each independently hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or substituted silyl.
R ^{6 to} R ⁹ are each independently hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or substituted silyl;
Ar ^{1 to} Ar ⁵ are each independently hydrogen, aryl having 6 to 30 carbon atoms, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or substituted silyl,
Ar ^{6 to} Ar ⁸ are each independently hydrogen, aryl having 6 to 30 carbon atoms, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or substituted silyl,
Ar ^{9 to} Ar ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or substituted silyl, and ,
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium;
The compound according to the above [1].

[3] R ^{1 to} R ⁵ are each independently silyl substituted with hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 3 to 8 carbons, or alkyl having 1 to 6 carbons. Yes,
R ^{6 to} R ⁹ are each independently hydrogen, alkyl having 1 to 12 carbons,
Ar ^{1 to} Ar ⁵ are each independently substituted with hydrogen, aryl having 6 to 18 carbon atoms, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, or alkyl having 1 to 6 carbon atoms. Has been Cyril,
Ar ^{6 to} Ar ⁸ are each independently hydrogen, aryl having 6 to 18 carbon atoms, or alkyl having 1 to 12 carbon atoms,
Ar ^{9 to} Ar ¹¹ are each independently hydrogen or alkyl having 1 to 12 carbons,
The compound according to the above [1].

[4] R ^{1 to} R ⁵ are each independently silyl substituted with hydrogen, alkyl having 1 to 4 carbon atoms, cyclohexyl, or alkyl having 1 to 4 carbon atoms,
R ^{6 to} R ⁹ are hydrogen,
Ar ^{1 to} Ar ⁵ are each independently hydrogen, aryl having 6 to 18 carbon atoms, alkyl having 1 to 4 carbon atoms, cyclohexyl, or silyl substituted with alkyl having 1 to 4 carbon atoms,
Ar ^{6 to} Ar ⁸ are each independently hydrogen, aryl having 6 to 18 carbon atoms,
Ar ^{9 to} Ar ¹¹ are hydrogen,
The compound according to the above [1].

[5] The compound according to the above [1], which is a compound represented by the following formula (1-1), formula (1-3), formula (1-35) or formula (1-81).

[6] A light emitting layer material containing the 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 embodiment of the present invention, it is possible to provide an anthracene-based compound that can be used as a light emitting layer material having an excellent device lifetime when applied to an organic EL device. In addition, the anthracene compound according to the present invention is a compound having a different chemical structure from that of the conventional one, and the options for the light emitting layer material can be increased. Furthermore, an excellent display device, lighting device, and the like can be provided by using an organic EL element having this characteristic.

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

1. First, the anthracene compound represented by the general formula (1) will be described in detail. The compound of the present invention is a compound in which phenyl and naphthyl are bonded to the 9-position and the 10-position, respectively, and a specific aryl is substituted at the 8-position of naphthyl (which is bonded to anthracene at the 2-position). By selecting such a substitution position and an aryl structure, the compound has achieved a device lifetime that is superior as a material for a light emitting layer, for example, while having a chemical structure different from the conventional one.

  As described above, Patent Document 3 discloses a material having naphthalene as a basic skeleton (including a compound in which anthracene is bonded to naphthalene), and Patent Document 4 discloses a bulky group at the 6th or 7th position of naphthyl bonded to anthracene. Is disclosed, and Patent Document 5 discloses a compound characterized by substituting aryl at the 7-position of naphthyl bonded to anthracene. However, the compound represented by the general formula (1) has excellent organic EL characteristics when applied to an organic EL element, compared to these known compounds.

The “alkyl” of “optionally substituted alkyl” in R ^{1 to} R ⁹ of the general formula (1) may be either a straight chain or a branched chain, for example, a linear alkyl having 1 to 24 carbon atoms. Alternatively, branched chain alkyl having 3 to 24 carbon atoms is exemplified. Preferred “alkyl” is alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

  Specific examples of “alkyl” 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, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hept Decyl, n- octadecyl, such as n- eicosyl, and the like.

  The substituent for alkyl in “optionally substituted alkyl” will be described later.

Examples of “cycloalkyl” of “optionally substituted cycloalkyl” in R ^{1 to} R ⁹ of the general formula (1) include cycloalkyl having 3 to 12 carbon atoms. Preferred “cycloalkyl” is cycloalkyl having 3 to 10 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 6 carbon atoms. Specific “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

  The substituent for cycloalkyl in the “optionally substituted cycloalkyl” will be described later, and in particular, a substituent such as alkyl can be mentioned. The substituted cycloalkyl is specifically methylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl or the like.

As “optionally substituted silyl” in R ^{1 to} R ⁹ of the general formula (1), unsubstituted silyl (—SiH ₃ ) and three hydrogens in the silyl are each independently selected from the above. Examples thereof include those substituted with alkyl, the above cycloalkyl, aryl described below, and the like. In particular, the three hydrogens in silyl are each independently substituted with methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenylyl or naphthyl, etc. The thing that is.

  Specific examples of “substituted silyl” include trimethylsilyl, triethylsilyl, tripropylsilyl, trii-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i -Propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl , Methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldii-propylsilyl, ethyldipropyl Pirushiriru, butyl di i- propyl silyl, sec- butyl di i- propyl silyl include trialkylsilyl such as t- butyldi i- propyl silyl. In addition, phenyldimethylsilyl, phenyldiethylsilyl, phenyldi-t-butylsilyl, methyldiphenylsilyl, ethyldiphenylsilyl, propyldiphenylsilyl, i-propyldiphenylsilyl, butyldiphenylsilyl, sec-butyldiphenylsilyl, t-butyldiphenylsilyl, tri And phenylsilyl.

With regard to “optionally substituted alkyl”, “optionally substituted cycloalkyl”, and “optionally substituted silyl” in Ar ^{1 to} Ar ¹¹ of the general formula (1), R ^{1 to} R The explanation in ⁹ can be cited.

Examples of “aryl” in “optionally substituted aryl” in Ar ^{1 to} Ar ¹¹ in the general formula (1) include aryl having 6 to 30 carbon atoms. Preferred “aryl” is aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms.

  Specific examples of “aryl” include monocyclic aryl phenyl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-) xylyl, mesityl, (o-, m-, p-) cumenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, fused bicyclic aryl Certain (1-, 2-) naphthyl, tricyclic aryl terphenylyl (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-ter Enyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), a condensed tricyclic aryl, acenaphthylene- (1-, 3- , 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'- Phenyl-m-terphenyl-4-yl, m-quaterphenyl), triphenylene- (1-, 2-) yl which is a fused tetracyclic aryl, pyrene- (1-, 2-, 4-) yl, Naphtacene- (1-, 2-, 5-) yl, pericyclic, a fused pentacyclic aryl Emissions - (1-, 2-, 3-) yl, pentacene - (1-, 2-, 5-, 6-) yl, and the like.

  Particularly preferred “aryl” are phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, and triphenylenyl, and among these, phenyl, biphenylyl, naphthyl, and naphthyl are preferred.

Examples of the substituent of “optionally substituted” in R ^{1 to} R ⁹ and Ar ^{1 to} Ar ¹¹ in the general formula (1) include alkyl, cycloalkyl, aryl, and fluorine. ^as, respectively as mentioned in the description of the "alkyl" for R 1 to R ^9, those mentioned in the description of the "cycloalkyl" in R 1 to R ^9, in the column of "aryl" in Ar 1 ^{to Ar 11} What you explained.

R ^{1 to} R ⁹ and Ar ^{1 to} Ar ¹¹ preferably have no “substituent”, but when having a substituent, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl , Isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl, n-nonyl, n-decyl, n-undecyl , N-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and other alkyls; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyls Phenyl, biphenylyl, naphthyl, terphenylyl, phenanthryl Aryl; methylphenyl, ethylphenyl, s-butylphenyl, t-butylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 1,6-dimethylnaphthyl, 2,6-dimethylnaphthyl, 4-t-butylnaphthyl, etc. Of alkylaryl; fluorine and the like. The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

Further, hydrogen in the anthracene skeleton constituting the compound represented by the general formula (1), hydrogen in phenyl or naphthyl substituted at the 9th or 10th position of anthracene, R ^{1 to} R ⁹ and Ar ^{1 to} Ar ¹¹ All or some of the hydrogens in may be deuterium.

  Specific examples of the compound represented by the above formula (1) include, for example, compounds represented by the following formula (1-1) to formula (1-631). Among the following compounds, the following formula (1-1), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-9), formula ( 1-10), Formula (1-15), Formula (1-16), Formula (1-18), Formula (1-19), Formula (1-21), Formula (1-22), Formula (1) -24), formula (1-25), formula (1-27) to formula (1-35), formula (1-38), formula (1-50), formula (1-53), formula (1- 58), formula (1-73), formula (1-76), formula (1-81), formula (1-127), formula (1-173), formula (1-175), formula (1-176) ), Formula (1-188), formula (1-190), formula (1-191), formula (1-195), formula (1-196), formula (1-198), formula (1-199). , Formula (1-210), Formula (1-211), Formula (1-213), Formula (1-214), (1-218), Formula (1-219), Formula (1-221), Formula (1-222), Formula (1-233), Formula (1-234), Formula (1-236), Formula ( 1-237), Formula (1-241), Formula (1-242), Formula (1-244), Formula (1-245), Formula (1-256), Formula (1-257), Formula (1) -259), Formula (1-260), Formula (1-264), Formula (1-313), Formula (1-315), Formula (1-316), Formula (1-327), Formula (1- 328), Formula (1-330), Formula (1-331), Formula (1-335), Formula (1-336), Formula (1-338), Formula (1-339), Formula (1-350) ), Formula (1-351), Formula (1-353), Formula (1-354), Formula (1-358), Formula (1-359), Formula (1-361), Formula (1-362) , Formula (1-373), (1-374), Formula (1-376), Formula (1-377), Formula (1-381), Formula (1-382), Formula (1-384), Formula (1-385), Formula ( 1-396), Formula (1-397), Formula (1-399), Formula (1-400), Formula (1-404), Formula (1-405), Formula (1-407), Formula (1) -408), formula (1-419), formula (1-420), formula (1-422), formula (1-423), formula (1-427), formula (1-470), formula (1- 472), Formula (1-473), Formula (1-484), Formula (1-485), Formula (1-487), Formula (1-488), Formula (1-498), Formula (1-499). ), Formula (1-500) to formula (1-502), formula (1-564), formula (1-566), formula (1-567), formula (1-569), formula (1-570) , Formula (1-572) to Formula (1-574), Formula (1-597), Formula (1-599), Formula (1-600), Formula (1-602), Formula (1-603), Formula (1-605) to Formula ( 1-607), formula (1-611) to formula (1-616), or a compound represented by formula (1-621) to formula (1-623) is preferable.

2. Production method of anthracene compound represented by formula (1) The anthracene compound represented by formula (1) can be produced by using a known synthesis method. For example, it can be synthesized according to the route shown in the following reactions (A-1) to (A-4).

In the reaction (A-1), 1-bromonaphthalene-2,7-diol can be synthesized by brominating 2,7-naphthalenediol with a brominating agent. In the following chemical structure, the representation of the naphthalene substituents Ar ^{6 to} Ar ¹¹ is omitted.

Next, in the reaction (A-2), 1-bromonaphthalene-2,7-diol is subjected to a Suzuki coupling reaction with 1 equivalent of phenylboronic acid in the presence of a base using a palladium catalyst, whereby phenyl is reacted. It is possible to synthesize naphthalenediol derivatives. In the following chemical structure, the representation of the naphthalene substituents Ar ^{6 to} Ar ¹¹ and the phenyl substituents Ar ^{1 to} Ar ⁵ are omitted.

Next, in the reaction (A-3), a naphthalene ditriflate derivative having a phenyl can be synthesized by reacting a naphthalene diol derivative having a phenyl with a trifluoromethanesulfonic anhydride in the presence of a base.

Finally, reaction (A-4) is represented by the general formula (1) by reacting a phenylanthraceneboronic acid derivative with a naphthaleneditriflate derivative having phenyl in the presence of a base using a palladium catalyst. Anthracene compounds can be synthesized. In the following chemical structure, the anthracene and its phenyl substituents R ^{1 to} R ⁹ and naphthalene and its phenyl substituents Ar ^{1 to} Ar ¹¹ are not shown.

As for the compounds having anthracene and its phenyl substituents R ^{1 to} R ⁹ , naphthalene and its phenyl substituents Ar ^{1 to} Ar ¹¹ , the raw materials used in the above reactions (A-1) to (A-4) It can be synthesized by using those having these substituents, or using those having a reactive functional group at the position corresponding to the substituent and bonding those substituents at an appropriate timing. In the above reaction (A-4), a final compound in which one of the two triflates of the naphthalene ditriflate derivative is present as a residue may be produced. A substituent is added to the triflate residue of such a compound. , A compound having a substituent (Ar ⁶ ) not only at the 8-position but also at the 7-position of naphthalene can be synthesized.

As the brominating agent and solvent used in the above reaction (A-1), and the reaction temperature, materials and conditions used in the conventional bromination reaction can be used. Examples of the brominating agent include N-bromosuccinimide (NBS), Br ₂ , Bu ₄ N ⁺ · Br ₃ ⁻ , KBr / H ₂ O ₂ , NaBr / NaBrO _3, and the like. Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, acetic acid, ethyl acetate, ethanol, dichlorobenzene, CH ₂ Cl ₂ , CHCl ₃ , CCl ₄ , and CH ₃ CN. These solvents may be used alone or as a mixed solvent. The reaction temperature is usually in the range of −10 to 130 ° C., more preferably 0 to 60 ° C.

When a palladium catalyst is used in the reaction (A-2) and the reaction (A-4) described above, for example, tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) Dichloropalladium (II): PdCl ₂ (PPh ₃ ) ₂ , palladium acetate (II): Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) ) Palladium (0) chloroform complex: Pd ₂ (dba) ₃ .CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tri-t-butylphosphino) palladium (0): Pd (P (t-Bu) ₃ ) ₂ , [1,1′-bis (diphenylphosphino) fe Locene] palladium (II) dichloride dichloromethane complex (1: 1): PdCl ₂ (dppf) · CH ₂ Cl ₂ , or bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (Pd (Amphos) Cl ₂ 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: t-Bu ₃ P, tricyclohexylphosphine: PCy ₃ , 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) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1 , 1′-binaphthyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, 2-and the like (dicyclohexyl phosphino) biphenyl.

  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) and reaction (A-4) include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, N, Examples thereof include N-dimethylacetamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, ethanol, isopropyl alcohol, t-butyl alcohol, and cyclopentyl methyl ether. These solvents may be used alone or as a mixed solvent. The reaction is usually carried out in the temperature range of 20 to 180 ° C, more preferably 60 to 130 ° C.

  When a base is used in the reaction (A-3), for example, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium acetate, potassium acetate, phosphorus Tripotassium acid, potassium fluoride, cesium fluoride, trimethylamine, triethylamine, pyridine and the like can be used.

Examples of the solvent used in the reaction (A-3) include pyridine, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, CH ₂ Cl ₂ , CHCl ₃ CH ₃ CN, and the like. It is done. 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.

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

3. Organic electroluminescent device The anthracene compound represented by the general formula (1) can be used as a material of an organic electroluminescent device, for example. 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 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-1,1′-diamine, ^4, N ^{4 '-} diphenyl ^{-N 4,} N ^4' - bis (9-phenyl -9H- carbazol-3-yl) - [1,1'-biphenyl] ^{-4,4'-diamine, N} 4, N ^4, N ^{4 ',} N ^4' - tetramethyl [1,1'-biphenyl] -4-yl) - [1,1'-biphenyl] -4,4'-diamine, 4,4 ', 4 "- tris (Triphenylamine derivatives such as (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives And thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7, 0,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonates, styrene derivatives, polyvinylcarbazole, polysilanes, etc. having the above monomers in the side chain are preferred, but light emission There is no particular limitation as long as it is a compound that can form a thin film necessary for manufacturing the device, inject holes from the anode, and further transport holes.

  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 anthracene compound represented by the general 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 anthracene compound represented by the general formula (1) 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.

  Examples of the host material that can be used in combination with the anthracene compound represented by the general formula (1) include fused ring derivatives such as anthracene and pyrene, bisstyrylanthracene derivatives and distyrylbenzene, which have been known as light emitters. Examples thereof include bisstyryl derivatives such as 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, benzothiazole derivatives, benzimidazole derivatives, benzotriazole 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-benzothiazolylcoumarin derivatives, 3 -Benzimidazolyl coumarin derivatives, coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, Nin derivatives, oxobenzoanthracene 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 the green to yellow dopant material 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 The compound which introduce | transduced the substituent which enables long wavelength, such as aryl, heteroaryl, aryl vinyl, amino, and cyano to the compound illustrated as a blue-green dopant material is also mentioned as 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 Substituents that enable longer wavelengths such as aryl, heteroaryl, arylvinyl, amino, and cyano are added to the compounds exemplified as the above-mentioned blue to blue-green and green to yellow dopant materials. The introduced compound 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.

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.

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.

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, fluorene, benzofluorene 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 more preferably aromatic amine derivatives wherein n is 2 and n is 2.

  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.

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, benzo Imidazole derivatives (such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole 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.

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.

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. Further, carbon 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′-pyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Pyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-pyridin-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-pyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilole, 9,10-di (2,2′-pyridine-6) -Yl) anthracene, 9,10-di (2,2'-pyridin-5-yl) anthracene, 9,10-di (2,3'-pyridin-6-yl) anthracene, 9,10-di (2 , 3′-Pyridin-5-yl) anthracene, 9,10-di (2,3′-pyridine) -Yl) -2-phenylanthracene, 9,10-di (2,3'-pyridin-5-yl) -2-phenylanthracene, 9,10-di (2,2'-pyridin-6-yl)- 2-phenylanthracene, 9,10-di (2,2′-pyridin-5-yl) -2-phenylanthracene, 9,10-di (2,4′-pyridin-6-yl) -2-phenylanthracene 9,10-di (2,4′-pyridin-5-yl) -2-phenylanthracene, 9,10-di (3,4′-pyridin-6-yl) -2-phenylanthracene, 9,10 -Di (3,4'-pyridin-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2'-pyridin-6-yl) thiophene, 3,4-diphenyl -2,5-di (2,3'-pyridine 5-yl) thiophene, 6'6 "- di (2-pyridyl) 2,2 ': 4', 4": 2 ", 2" '- like quaterphenyl pyridine.

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.

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 at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X is an optionally substituted arylene, and Y is Optionally substituted aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazolyl, and n is each independently an integer of 0 to 3.

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 at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen, alkyl, At least one of optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring, or cyano, and X ¹ is optionally substituted arylene having 20 or less carbon atoms. Each of n is independently an integer of 0 to 3, and each of m is independently an integer of 0 to 4.

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.

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 at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, and X ¹ is an optionally substituted arylene having 20 or less carbon atoms. And n is each independently an integer of 0 to 3.

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.

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 at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, and X ¹ is an optionally substituted arylene having 10 or less carbon atoms. Y ¹ is optionally substituted aryl having 14 or less carbon atoms, and n is independently an integer of 0 to 3.

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.

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 boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature −150 to + 300 ° C., film thickness 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, etc.

  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 for personal computers where thinning is an issue, considering that conventional methods consist 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.

  The present invention will be described in more detail based on examples. First, synthesis examples of anthracene compounds used in Examples are described below.

[Synthesis Example 1] Synthesis of Compound (1-1)

<Synthesis of 1-bromonaphthalene-2,7-diol>
Under a nitrogen atmosphere, naphthalene-2,7-diol (30 g), chloroform (450 ml) and acetic acid (180 ml) were placed in a flask and stirred for 5 minutes. Thereafter, 33.34 g of N-bromosuccinimide (NBS) was added at room temperature and stirred for 2 hours. After the reaction, saturated brine (200 ml) was added. Next, the reaction mixture was extracted with chloroform, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by short column chromatography on silica gel (solvent: toluene / acetic acid). Ethyl = 6/1 (volume ratio)) to obtain 42.8 g (yield: 95.5%) of 1-bromonaphthalene-2,7-diol.

<Synthesis of 1-phenylnaphthalene-2,7-diol>
Under a nitrogen atmosphere, 1-bromonaphthalene-2,7-diol (36 g), phenylboronic acid (36.72 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 5.22 g), Sodium carbonate (47.88 g), toluene (360 ml) and t-butyl alcohol (180 ml) were placed in the flask and stirred for 5 minutes. Then, water (72 ml) was added and refluxed for 4 hours. After completion of the heating, the reaction solution was cooled and water (200 ml) was added. Thereafter, the reaction mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the crude product obtained was column purified on silica gel (solvent: ethyl acetate / toluene). = 1/10 (volume ratio)) to obtain 25 g (yield: 70.3%) of 1-phenylnaphthalene-2,7-diol.

<Synthesis of 1-phenylnaphthalene-2,7-diyl bis (trifluoromethanesulfonate)>
In a nitrogen atmosphere, 1-phenylnaphthalene-2,7-diol (22 g) and pyridine (176 ml) were placed in a flask, cooled to 0 ° C., and then trifluoromethanesulfonic anhydride (Tf ₂ O, 105.1 g) was added. Slowly dripped. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. After the reaction, water (200 ml) was added. Next, the reaction mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the crude product obtained was subjected to column purification with silica gel (solvent: toluene). As a result, 46.7 g (yield: 100%) of 1-phenylnaphthalene-2,7-diyl bis (trifluoromethanesulfonate) was obtained.

<Compound (1-1): Synthesis of 9-phenyl-10- (8-phenylnaphthalen-2-yl) anthracene>
Under a nitrogen atmosphere, 1-phenylnaphthalene-2,7-diyl bis (trifluoromethanesulfonate) (4.4 g), (10-phenylanthracen-9-yl) boronic acid (2.6 g), bis (dibenzylideneacetone) ) Palladium (0) (Pd (dba) ₂ , 0.25 g), tricyclohexylphosphine (PCy ₃ , 0.18 g), tripotassium phosphate (3.7 g), toluene (40 ml) and ethanol (10 ml) were flasked. And stirred for 5 minutes. Then, water (5 ml) was added and refluxed for 3 hours. After completion of heating, the reaction solution was cooled and water (50 ml) was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, and the crude product obtained by distilling off the solvent under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 6). / 1 (volume ratio)), and reprecipitation was performed with ethyl acetate. Next, reprecipitation was performed with heptane, and further purification by sublimation was performed to obtain 0.88 g (yield) of 9-phenyl-10- (8-phenylnaphthalen-2-yl) anthracene as the target compound (1-1). Rate: 22%).

The structure of the objective compound (1-1) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.15 (d, 1H), 8.06 (s, 1H), 8.04 (d, 1H), 7.71 to 7.45 (m, 14H) 7.37-7.26 (m, 7H).

The glass transition temperature (Tg) of the target compound (1-1) was 105.8 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

[Synthesis Example 2] Synthesis of Compound (1-3)

<Synthesis of 1-([1,1′-biphenyl] -3-yl) naphthalene-2,7-diol>
Under a nitrogen atmosphere, 1-bromonaphthalene-2,7-diol (12 g), 3-biphenylboronic acid (14.91 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 2.32 g ), Sodium carbonate (15.96 g), toluene (120 ml) and t-butyl alcohol (60 ml) were placed in a flask and stirred for 5 minutes. Then, water (24 ml) was added and refluxed for 4 hours. The reaction liquid was cooled after completion | finish of a heating, and water (100 ml) was added. Thereafter, the reaction mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the crude product obtained was column purified on silica gel (solvent: ethyl acetate / toluene). = 1/10 (volume ratio)) to obtain 12 g (yield: 76.5%) of 1-([1,1′-biphenyl] -3-yl) naphthalene-2,7-diol.

<Synthesis of 1-([1,1′-biphenyl] -3-yl) naphthalene-2,7-diyl bis (trifluoromethanesulfonate)>
Under a nitrogen atmosphere, 1-([1,1′-biphenyl] -3-yl) naphthalene-2,7-diol (12 g) and pyridine (96 ml) were placed in a flask, cooled to 0 ° C., and then trifluoromethanesulfone. Acid anhydride (Tf ₂ O, 43.36 g) was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. After the reaction, water (100 ml) was added. Next, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the crude product obtained was subjected to column purification with silica gel (solvent: toluene / heptane = 1/3 (volume ratio)) and 15.5 g of 1-([1,1′-biphenyl] -3-yl) naphthalene-2,7-diyl bis (trifluoromethanesulfonate) (yield: 70%).

<Compound (1-3): Synthesis of 9- (8-([1,1′-biphenyl] -3-yl) naphthalen-2-yl) -10-phenylanthracene>
1-([1,1′-biphenyl] -3-yl) naphthalene-2,7-diyl bis (trifluoromethanesulfonate) (5.76 g), (10-phenylanthracen-9-yl) under nitrogen atmosphere Boronic acid (2.98 g), bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ , 0.17 g), tricyclohexylphosphine (PCy ₃ , 0.12 g), tripotassium phosphate (4.24 g) ), Toluene (40 ml) and ethanol (10 ml) were placed in a flask and stirred for 5 minutes. Then, water (5 ml) was added and refluxed for 3 hours. After completion of heating, the reaction solution was cooled and water (50 ml) was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, and the crude product obtained by distilling off the solvent under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 6). / 1 (volume ratio)), and reprecipitation was performed with ethyl acetate. Next, reprecipitation is performed with heptane, and further purification by sublimation is performed to obtain 9- (8-([1,1′-biphenyl] -3-yl) naphthalene-2-2, which is the target compound (1-3). Yl) -10-phenylanthracene (3.3 g, yield: 62%) was obtained.

The structure of the target compound (1-3) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.17 (d, 1H), 8.16 (s, 1H), 8.07 (d, 1H), 7.78-7.74 (m, 3H) 7.70-7.66 (m, 4H), 7.61-7.41 (m, 11H), 7.35-7.27 (m, 7H).

[Synthesis Example 3] Synthesis of Compound (1-35)

<Synthesis of 1-phenyl-7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate>
In a nitrogen atmosphere, 1-phenylnaphthalene-2,7-diyl bis (trifluoromethanesulfonate) (10 g), (10-phenylanthracen-9-yl) boronic acid (6.55 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 0.69 g), tripotassium phosphate (8.48 g), tetrahydrofuran (80 ml) and isopropyl alcohol (20 ml) were placed in a flask and stirred for 5 minutes. Then, water (5 ml) was added and reacted at 65 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled and water (50 ml) was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the crude product obtained was subjected to column purification with silica gel (solvent: heptane / toluene = 10 / 1 (volume ratio)), and then reprecipitated with methanol to obtain 6.1 g (yield) of 1-phenyl-7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate. Rate: 50.8%).

<Compound (1-35): Synthesis of 9- (7,8-diphenylnaphthalen-2-yl) -10-phenylanthracene>
In a nitrogen atmosphere, 1-phenyl-7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate (3 g), phenylboronic acid (0.91 g), tetrakis (triphenylphosphine) palladium ( 0) (Pd (PPh ₃ ) ₄ , 0.17 g), tripotassium phosphate (2.11 g), 1,2,4-trimethylbenzene (18 ml) and t-butyl alcohol (3 ml) in a flask Stir for minutes. Then, water (3 ml) was added and refluxed for 8 hours. After completion of the heating, the reaction solution was cooled and water (20 ml) was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, and the crude product obtained by distilling off the solvent under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 6). / 1 (volume ratio)), and then reprecipitated with ethyl acetate. Next, reprecipitation was performed with heptane, and further sublimation purification was performed to obtain 1.05 g of 9- (7,8-diphenylnaphthalen-2-yl) -10-phenylanthracene, which is the target compound (1-35). (Yield: 40%) was obtained.

The structure of the objective compound (1-35) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.17 (d, 1H), 8.12 (d, 1H), 7.85 (s, 1H), 7.72-7.67 (m, 5H) , 7.63 to 7.53 (m, 4H), 7.49 to 7.44 (m, 2H), 7.33 to 7.28 (m, 4H), 7.22 to 7.07 (m, 10H).

The glass transition temperature (Tg) of the target compound (1-35) was 131.3 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

[Synthesis Example 4] Synthesis of Compound (1-81)

<Compound (1-81): Synthesis of 9-phenyl-10- (1-phenyl- [2,2′-binaphthalene] -7-yl) anthracene>
1-phenyl-7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate (3 g), 2-naphthaleneboronic acid (1.28 g), tetrakis (triphenylphosphine) under nitrogen atmosphere Palladium (0) (Pd (PPh ₃ ) ₄ , 0.17 g), tripotassium phosphate (2.11 g), 1,2,4-trimethylbenzene (18 ml) and t-butyl alcohol (3 ml) are placed in a flask. And stirred for 5 minutes. Then, water (3 ml) was added and refluxed for 8 hours. After the heating, the reaction solution was cooled, methanol (20 ml) was added, and the precipitate was filtered. The precipitate was further washed with methanol and water to obtain a crude product of the target compound (1-81). The crude product was subjected to short column purification with silica gel (solvent: toluene) and then reprecipitated with ethyl acetate. Next, reprecipitation with heptane was performed, and further purification by sublimation was performed to obtain 9-phenyl-10- (1-phenyl- [2,2′-binaphthalene] -7-yl which is the target compound (1-81). ) 2.1 g (yield: 72.3%) of anthracene was obtained.

The structure of the objective compound (1-81) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.18 (d, 1H), 8.14 (d, 1H), 7.88 (s, 1H), 7.80 (d, 1H), 7.77 To 7.74 (m, 3H), 7.70 to 7.67 (m, 4H), 7.64 to 7.55 (m, 5H), 7.49 to 7.43 (m, 4H), 7 .33 to 7.30 (m, 4H), 7.26 to 7.23 (m, 3H), 7.12 to 7.05 (m, 3H).

The glass transition temperature (Tg) of the target compound (1-81) was 140.7 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

[Synthesis Example 5] Synthesis of Compound (D)

<Synthesis of naphthalene-1,7-diyl bis (trifluoromethanesulfonate)>
Under a nitrogen atmosphere, naphthalene-1,7-diol (25 g) and pyridine (500 ml) were placed in a flask, cooled to 0 ° C., and then trifluoromethanesulfonic anhydride (Tf ₂ O, 110.1 g) was slowly added dropwise. . Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. After the reaction, water (300 ml) was added. Next, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was subjected to column purification with silica gel (solvent: heptane / toluene = 3/1 (volume ratio)) to obtain 64.9 g (yield: 98%) of naphthalene-1,7-diyl bis (trifluoromethanesulfonate).

<Synthesis of 7- (10-Phenylanthracen-9-yl) naphthalen-1-yl trifluoromethanesulfonate>
Under a nitrogen atmosphere, naphthalene-1,7-diyl bis (trifluoromethanesulfonate) (10 g), (10-phenylanthracen-9-yl) boronic acid (7.03 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 0.82 g), potassium carbonate (6.51 g), tetrahydrofuran (80 ml) and isopropyl alcohol (20 ml) were placed in a flask and refluxed for 3 hours with stirring. After completion of heating, the reaction solution was cooled and water (50 ml) was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, and the crude product obtained by distilling off the solvent under reduced pressure was subjected to column purification with silica gel (solvent: heptane / toluene = 6). / 1 (volume ratio)) to obtain 4.2 g (yield: 34%) of 7- (10-phenylanthracen-9-yl) naphthalen-1-yl trifluoromethanesulfonate.

<Compound (D): Synthesis of 9-([1,2'-Binaphthalene] -7-yl) -10-phenylanthracene>
Under a nitrogen atmosphere, 7- (10-phenylanthracen-9-yl) naphthalen-1-yl trifluoromethanesulfonate (3.5 g), 2-naphthaleneboronic acid (1.25 g), bis (di-t-butyl ( 4-Dimethylaminophenyl) phosphine) dichloropalladium (II) (Pd (amphos) Cl ₂ , 0.09 g), potassium carbonate (1.83 g), tetrabutylammonium bromide (0.09 g) and toluene (30 ml). The flask was stirred for 5 minutes. Then, water (6 ml) was added and refluxed for 8 hours. After completion of the heating, the reaction solution was cooled and water (20 ml) was added. Thereafter, the reaction mixture was extracted with toluene, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was subjected to short column purification (solvent: toluene) with silica gel. After that, recrystallization was performed with ethyl acetate. Further, purification by sublimation yielded 0.97 g (yield: 29%) of 9-([1,2′-binaphthalene] -7-yl) -10-phenylanthracene, which was the target compound (D).

The structure of the target compound (D) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.17 (d, 1H), 8.08 (s, 1H), 8.06 (d, 1H), 7.98 (s, 1H), 7.81 To 7.77 (m, 3H), 7.72 to 7.50 (m, 11H), 7.47 to 7.39 (m, 4H), 7.31 to 7.27 (m, 4H).

The glass transition temperature (Tg) of the target compound (D) was 120 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

<Evaluation of organic EL element>
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.

An organic EL device according to Example 1 and Comparative Examples 1 to 3 was prepared, and voltage (V), EL emission wavelength (nm), and external quantum efficiency (%), which are characteristics at the time of 1000 cd / m ² emission, were measured. Next, the time for maintaining a luminance of 80% (1600 cd / m ² ) or more of the initial luminance when driving at a constant current at a current density at which a luminance of 2000 cd / m ² was obtained was measured. Hereinafter, examples and comparative examples will be described in detail.

  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-3AR 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 Examples 1 to 3.

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, “HI2” is 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, “HT” is N ⁴ , N ⁴ , N ^{4 ′} , N ^{4 ′} -tetra [1,1′-biphenyl] -4-yl)-[1,1′-biphenyl] -4,4′-diamine, compound (A) is 9- (naphthalene- 2-yl) -10-phenylanthracene, compound (B) is 9-phenyl-10- (6-phenylnaphthalen-2-yl) anthracene, and compound (C) is 9-phenyl-10- (4-phenylnaphthalene- 1-yl) anthracene, “BD1” is 7,7-di Methyl-N ⁵ , N ⁹ -diphenyl-N ⁵ , N ⁹ -bis (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluorene-5,9-diamine, “ET1” is 4,4 ′-( (2-Phenylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine. The chemical structure is shown below together with quinolinol lithium (Liq).

<Example 1>
<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 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 HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat containing compound (1-1) of the present invention, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing ET1, molybdenum vapor deposition vessel containing Liq A boat, a molybdenum vapor deposition boat containing magnesium, 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 is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer, and HI 2 The deposition boat containing is heated and deposited to a film thickness of 5 nm to form a second hole injection layer, and then the deposition boat containing HT is heated to a film thickness of 20 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing the compound (1-1) of the present invention 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 25 nm. The deposition rate was adjusted so that the weight ratio of compound (1-1) 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 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. Met. In addition, as a result of performing 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 luminance was 267 hours.

<Comparative Example 1>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (A). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 4.2 V and the external quantum efficiency was 3.7% (blue emission with a wavelength of about 458 nm). The time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 46 hours.

<Comparative example 2>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (B). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the drive voltage was 3.9 V and the external quantum efficiency was 5.0% (blue emission with a wavelength of about 457 nm). Further, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 130 hours.

<Comparative Example 3>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (C). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 4.1 V and the external quantum efficiency was 4.7% (blue emission with a wavelength of about 456 nm). In addition, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 152 hours.

The above results are summarized in Table 2.

The organic EL elements according to Examples 2 to 6 and Comparative Examples 4 to 6 were prepared, and voltage (V), EL emission wavelength (nm), and external quantum efficiency (%), which are characteristics at 1000 cd / m ² emission, respectively. Then, the time for maintaining a luminance of 80% (1600 cd / m ² ) or more of the initial luminance when driven at a constant current at a current density at which a luminance of 2000 cd / m ² is obtained was measured. Hereinafter, examples and comparative examples will be described in detail.

  In the organic EL elements according to Examples 2 to 6 and Comparative Examples 4 to 6 produced, the material configurations of the respective layers are shown in Tables 3 to 5 below.

In Tables 3 to 5, “HT2” is N-([1,1′-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl). ) Phenyl) -9H-fluoren-3-amine, “NPD” is N ⁴ , N ^{4 ′} -di (naphthalen-1-yl) -N ⁴ , N ^{4 ′} -diphenyl- [1,1′-biphenyl]- 4,4′-diamine, compound (D) is 9-([1,2′-binaphthalene] -7-yl) -10-phenylanthracene, “BD2” is N ⁵ , N ⁹ , 7,7, -tetra Phenyl-N ⁵ , N ⁹ -bis (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluorene-5,9-diamine, “ET2” is 9- (4 ′ (dimesitylboranyl)-[ 1,1′-Binaphthalene] -4-yl) -9H-carbazole, “ET "Is 3- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) pyridine and" ET4 "is 2- (4- (9,10-di (naphthalen-2-yl) anthracene). 2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole. The chemical structure is shown below.

<Example 2>
<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 support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT2. Vapor deposition boat, molybdenum vapor deposition boat containing compound (1-1) of the present invention, molybdenum vapor deposition boat containing BD2, molybdenum vapor deposition boat containing ET2, molybdenum vapor deposition containing ET3 A boat, a molybdenum vapor deposition boat containing lithium fluoride (LiF), and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer, and HI 2 Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT2 is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing the compound (1-1) of the present invention 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 20 nm. The deposition rate was adjusted so that the weight ratio of compound (1-1) to BD2 was approximately 95: 5. Next, the vapor deposition boat containing ET2 was heated and vapor-deposited so as to have a film thickness of 10 nm to form a first electron transport layer. Next, the vapor deposition boat containing ET3 was heated and vapor-deposited to a film thickness of 20 nm to form a second electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing LiF was heated and evaporated 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 lithium fluoride / aluminum electrode as the cathode, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 3.89 V, the external quantum efficiency is 6.14% (blue emission with a wavelength of about 459 nm) Met. In addition, as a result of performing 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 235 hours. Note that the time for maintaining the luminance of 90% or more of the initial luminance was 57 hours.

<Comparative example 4>
<Element Using Compound (C) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (C). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 2, the driving voltage was 3.59 V and the external quantum efficiency was 6.17% (blue emission with a wavelength of about 458 nm). Further, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 116 hours. Note that the time for maintaining the luminance of 90% or more of the initial luminance was 25 hours.

<Example 3>
<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 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 HI2, a molybdenum vapor deposition boat containing NPD, the compound of the present invention (1 -1) Molybdenum vapor deposition boat, BD2 molybdenum vapor deposition boat, ET4 molybdenum vapor deposition boat, Liq molybdenum vapor deposition boat, magnesium vapor deposition molybdenum A molybdenum vapor deposition boat containing a boat and silver was attached.

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 2 was heated to deposit to a thickness of 10 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 60 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (1-1) of the present invention 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 30 nm. The deposition rate was adjusted so that the weight ratio of compound (1-1) to BD2 was approximately 95: 5. Next, a vapor deposition boat containing ET4 and a molybdenum vapor deposition boat containing Liq were heated at the same time so as to have a film thickness of 20 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of ET4 and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 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, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 4.46 V, the external quantum efficiency is 4.35% (blue emission with a wavelength of about 460 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 luminance was 383 hours. The time for maintaining the luminance of 90% or more of the initial luminance was 178 hours.

<Comparative Example 5>
<Element Using Compound (D) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 3 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (D). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 3, the drive voltage was 4.34 V and the external quantum efficiency was 3.89% (blue emission with a wavelength of about 461 nm). Further, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 251 hours. Note that the time for maintaining a luminance of 90% or more of the initial luminance was 91 hours.

<Example 4>
<Element Using Compound (1-1) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by a method according to Example 3 except that the mixture of ET4 and Liq, which is an electron transport material for the electron transport layer, was changed to ET1. When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 3, the driving voltage was 4.48 V and the external quantum efficiency was 4.32% (blue emission with a wavelength of about 461 nm). The time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 334 hours. Note that the time for maintaining the luminance of 90% or more of the initial luminance was 155 hours.

<Comparative Example 6>
<Element Using Compound (D) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 4 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (D). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 4, the driving voltage was 4.27 V and the external quantum efficiency was 3.84% (blue emission with a wavelength of about 461 nm). Further, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 223 hours. In addition, the time for maintaining the luminance of 90% or more of the initial luminance was 84 hours.

<Example 5>
<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 support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT2. Vapor deposition boat, molybdenum vapor deposition boat containing compound (1-1) of the present invention, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing ET1, molybdenum vapor deposition vessel containing Liq A boat, a molybdenum vapor deposition boat containing magnesium, 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 is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer, and HI 2 Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT2 is heated to a thickness of 20 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing the compound (1-1) of the present invention 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 25 nm. The deposition rate was adjusted so that the weight ratio of compound (1-1) 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 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. Met. In addition, as a result of performing a constant current driving test with a current density for obtaining an initial 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 270 hours.

<Example 6>
<Element Using Compound (1-3) as Host Material for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-1) as the host material of the light emitting layer was changed to the compound (1-3). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 5, the driving voltage was 4.37 V and the external quantum efficiency was 4.60% (blue emission with a wavelength of about 458 nm). The time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 242 hours.

The above results are summarized in Table 6.

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

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 (9)

A compound represented by the following general formula (1).
In formula (1),
R ^{1 to} R ⁵ are each independently silyl substituted with hydrogen, alkyl having 1 to 4 carbons, cyclohexyl , or alkyl having 1 to 4 carbons ;
Ar ^{1 to} Ar ⁵ are each independently hydrogen, phenyl, biphenylyl, naphthyl , alkyl having 1 to 4 carbons, cyclohexyl , or silyl substituted with alkyl having 1 to 4 carbons , and
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium. The compound of Claim 1 which is a compound represented by a following formula (1-1) or a formula (1-3).
The material for light emitting layers containing the compound of Claim 1 or 2 . The organic electroluminescent element which has a pair of electrode which consists of an anode and a cathode, and the light emitting layer which is arrange | positioned between this pair of electrodes and contains the material for light emitting layers of Claim 3 . The organic electroluminescent element according to claim 4 , 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 element according to claim 4 or 5 , 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 6 . Display device comprising the organic electroluminescent device as claimed in any one of claims 4-7. Lighting device comprising the organic electroluminescent device as claimed in any one of claims 4-7.