JP5353233B2 - Anthracene derivative compound having pyridylphenyl group and organic electroluminescence device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent device that can be driven by a low driving voltage, and has improved stability and an improved luminescence life. <P>SOLUTION: The organic electroluminescent device is manufactured by employing an anthracene derivative compound comprising a pyridylphenyl group as its electron-transporting material. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an anthracene derivative compound having a pyridylphenyl group, an organic electroluminescent element using the same, a display device, and an illumination device.

  2. Description of the Related Art Conventionally, display devices using light emitting elements that emit electroluminescence have been studied variously because they can be reduced in power and thinned. Further, organic electroluminescent elements made of organic materials can be easily reduced in weight and size. Therefore, it has been actively studied. In particular, the development of organic materials with light emission characteristics such as blue, which is one of the three primary colors of light, and organic materials that have charge transporting ability (such as semiconductors and superconductors) such as holes and electrons The development of materials has been actively studied so far, regardless of whether it is a high molecular compound or a low molecular compound.

  For example, a method for synthesizing a compound having a pyridylphenyl structure in the molecule and an organic electroluminescent device using the compound in an organic compound layer have been reported (Japanese Patent Laid-Open No. 2003-282270 (Patent Document 1)). Patent Document 1 reports an organic electroluminescent device using a compound having a pyridylphenyl structure in the molecule as an electron transport material. An organic electroluminescent device using a compound in which an aryl-heteroaryl group such as a pyridyl group or a phenyl group is substituted on the central skeleton of anthracene has also been reported (Japanese Patent Laid-Open No. 2005-170911 (Patent Document 2)). No. 2003-146951 (Patent Document 3)).

JP 2003-282270 A Japanese Unexamined Patent Publication No. 2005-170911 JP 2003-146951 A

  As described above, several electron transport materials of compounds having a pyridylphenyl structure in the molecule and light emitting device materials of anthracene skeleton compounds are known. These known materials are electron transport materials (electron transport materials). In general, it is possible to form a stable electron transport layer and / or electron injection layer, which can reduce the driving voltage of the light emitting element, increase the element life, As a result, characteristics such as the ability to produce a stable light-emitting element are not sufficiently and well-balanced. Under such circumstances, development of an electron transport material having excellent driving voltage, lifetime and stability of the light emitting element is desired. In particular, for blue light-emitting elements, an electron transport material having superior characteristics compared to red and green light-emitting elements has not been obtained, and development of an electron transport material suitable for improving the characteristics of blue light-emitting elements is desired. ing.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have made the organic electroluminescence device provided with an organic layer containing a compound represented by the following general formula (1) as an electron transport material. The present inventors have found that an organic electroluminescent device excellent in driving voltage and excellent in balance between the lifetime and stability of the device can be obtained, and the present invention has been completed.

[1] A compound represented by the following general formula (1).
In formula (1),
R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl having 1 to 12 carbon atoms, optionally substituted cycloalkyl having 3 to 12 carbon atoms, or substituted. And optionally having 6 to 20 carbon atoms, and
Ar is each independently a group represented by any of the following formulas Ar1, Formula Ar2, Formula Ar3, Formula Ar4, Formula Ar5, or Formula Ar6.

[2] R ¹ is alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons or aryl having 6 to 20 carbons, R ² , R ³ and R ⁴ are hydrogen, and
Ar is a group represented by any one of formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6,
The compound described in [1] above.

[3] R ¹ is aryl having 6 to 20 carbon atoms,
R ² , R ³ and R ⁴ are hydrogen and
Ar is a group represented by any one of formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6,
The compound described in [1] above.

[4] R ¹ is phenyl, biphenylyl, terphenylyl, or naphthyl, R ² , R ^3, and R ⁴ are hydrogen, and
Ar is a group represented by any one of formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6,
The compound described in [1] above.

[5] The following formula (1-1), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-12), formula (1- 27) The compound described in the above [1], represented by formula (1-30) or formula (1-42).

[6] An electron transport material comprising the compound according to any one of [1] to [5].

[7] A pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the above [6] disposed between the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer.

[8] The above [7], wherein at least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. The organic electroluminescent element described in 1.

[9] At least one of the electron transport layer and the electron injection layer may further include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, Contains at least one selected from the group consisting of halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals The organic electroluminescent element as described in the above [8].

[10] A display device comprising the organic electroluminescent element according to any one of [7] to [9].

[11] An illumination device including the organic electroluminescent element according to any one of [7] to [9].

  According to the preferred embodiment of the present invention, an organic electroluminescent device excellent in the driving voltage characteristics can be obtained. In addition, since a preferable electron transport material of the present invention has a low crystallinity and can form a stable amorphous film, a stable electron transport layer and / or an electron injection layer can be formed. An element can be manufactured. Furthermore, since the preferable electron transport material of this invention has a high glass transition temperature (Tg), the light emitting element (or organic layer) excellent in heat resistance can be obtained. Therefore, according to the preferred embodiment of the present invention, not only an excellent driving voltage can be realized, but also the balance between the lifetime and stability of the light emitting element can be made excellent. Further, the preferred electron transport material of the present invention is particularly suitable for a blue light emitting element, and according to this electron transport material, a blue light emitting element having an element life comparable to a red or green light emitting element can be produced. Can do. Furthermore, by using this organic electroluminescent element, a high-performance display device such as a full color display can be obtained.

1. Compound represented by formula (1) The anthracene derivative compound having a pyridylphenyl group of the present invention will be described in detail. The anthracene derivative compound of the present invention is a compound represented by the above general formula (1).

R ¹ , R ² , R ³ and R ⁴ (hereinafter also referred to as “R ^{1 to} R ⁴ ”) in the formula (1) are each independently hydrogen and optionally substituted alkyl having 1 to 12 carbon atoms. , An optionally substituted cycloalkyl having 3 to 12 carbon atoms and an optionally substituted aryl having 6 to 20 carbon atoms can be appropriately selected. R ^{1 to} R ⁴ may be all the same or different, but preferably one or more of R ^{1 to} R ⁴ so that the compound represented by formula (1) has asymmetric property. Is selected differently from others. An example of this is when R ^{2 to} R ⁴ are hydrogen and R ¹ is a group other than hydrogen.

Regarding “optionally substituted alkyl having 1 to 12 carbon atoms” in R ^{1 to} R ⁴ of formula (1), “alkyl having 1 to 12 carbon atoms” may be either a straight chain or a branched chain. That is, it is a linear alkyl having 1 to 12 carbons or a branched alkyl having 3 to 12 carbons. Among these, C1-C6 alkyl (C3-C6 branched alkyl) is preferable. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

  Specific examples of “alkyl having 1 to 12 carbon atoms” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, and 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- Examples thereof include methyl decyl and n-dodecyl.

As for “optionally substituted cycloalkyl having 3 to 12 carbon atoms” in R ^{1 to} R ⁴ in formula (1), among “cycloalkyl having 3 to 12 carbon atoms”, cyclohexane having 3 to 10 carbon atoms. Alkyl is preferred. More preferably, it is a C3-C8 cycloalkyl, More preferably, it is a C3-C6 cycloalkyl.

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

Regarding “optionally substituted aryl having 6 to 20 carbon atoms” in R ^{1 to} R ⁴ in formula (1), among “aryl having 6 to 20 carbon atoms”, aryl having 6 to 16 carbon atoms is preferable. . More preferably, it is C6-C12 aryl.

  Specific examples of “C6-C20 aryl” include monocyclic aryl phenyl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5- , 2,6-, 3,4-, 3,5-) xylyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2 -, 3-, 4-) biphenylyl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl '-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-terfeny 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3), which are fused tricyclic aryls -, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, condensed tetracyclic aryl triphenylene- (1 -, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl, perylene- (1-, 2-) which is a fused pentacyclic aryl , 3-) Ill and the like.

  Preferred “aryl having 6 to 20 carbon atoms” is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl and m-terphenyl-5′-yl.

Examples of the “substituent” in R ^{1 to} R ⁴ in the formula (1) include alkyl, cycloalkyl, and aryl. Preferable examples among these are the same as those described in the “alkyl” column, the “cycloalkyl” column, and the “aryl” column in R ^{1 to} R ⁴ , respectively.

R ^{1 to} R ⁴ preferably have no “substituent”, but when it has 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, etc. Alkyl; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; aryl such as phenyl, biphenylyl, naphthyl, terphenylyl, phenanthryl, 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.

Specific examples of R ^{1 to} R ⁴ include the following groups. Examples of R in the structural formula include the same as those described in the column of “alkyl” in R ^{1 to} R ⁴ .

  The two Ar (pyridylphenyl groups) in formula (1) are each independently selected as appropriate from the groups represented by the following formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6 Can do. The numbers in the chemical structure are the position numbers of the respective ring atoms and have no other meaning. Ar is unsubstituted except that an anthracene skeleton is bonded. The pyridine ring in Ar is bonded to the 3rd or 4th position of the benzene ring (based on the anthracene bond position) to facilitate conjugation of the anthracene skeleton and the benzene ring, and any position of the pyridine ring ( 2nd, 3rd and 4th positions). Moreover, although two Ar of Formula (1) may be the same or different, it is preferable that they are the same.

  Specific examples of the compound represented by the general formula (1) include, for example, the following formulas (1-1) to (1-66) and formulas (1-201) to (1-215). Compounds. Among the following compounds, compounds represented by the following formula (1-1) to formula (1-48) are preferable, and in particular, the following formula (1-1) to formula (1-30) and formula (1-37) A compound represented by formula (1-42) is preferred. Further, the following formula (1-1), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-12), formula (1-27 ), A compound represented by formula (1-30) or formula (1-42) is more preferred.

2. Method for producing a compound represented by the general formula (1) Next, a method for manufacturing a compound of the present invention.
The compound of the present invention basically comprises a known compound and a known synthesis method such as Suzuki coupling reaction or Negishi coupling reaction (for example, “Metal-Catalyzed Cross-Coupling Reactions-Second, Completely Revised and It can be synthesized using “Enlarged Edition”. It can also be synthesized by combining both reactions. A scheme for synthesizing the compound represented by the general formula (1) by Suzuki coupling reaction or Negishi coupling reaction is illustrated below.

<Method for Synthesizing Compound Represented by General Formula (1) (Part 1)>
<Synthesis of 3-pyridyl-1-bromobenzene>
First, a zinc chloride complex of pyridine is synthesized by the following reaction formula (1), and then, a zinc chloride complex of pyridine and 1,3-dibromobenzene are reacted by the following reaction formula (2) to give 3- (4- Pyridyl) -1-bromobenzene can be synthesized. In the reaction formula (1), “ZnCl ₂ · TMEDA” is a tetramethylethylenediamine complex of zinc chloride. Here, the method for synthesizing 3- (4-pyridyl) -1-bromobenzene using 4-bromopyridine as a raw material is exemplified, but bromide can also be obtained by using 3-bromopyridine or 2-bromopyridine as a raw material. Instead, the corresponding target product, ie, 3- (3-pyridyl) -1-bromobenzene or 3- (2-pyridyl) -1-bromobenzene, can be obtained by using iodide. Moreover, although the synthesis method of 3- (4-pyridyl) -1-bromobenzene using 1,3-dibromobenzene as a raw material was illustrated here, by using 1,4-dibromobenzene as a raw material, By using iodide instead of bromide, the corresponding target product, 4- (4-pyridyl) -1-bromobenzene, can be obtained. Furthermore, compounds corresponding to Ar1 to Ar6 can be obtained by appropriately selecting raw materials.
Further, instead of reacting 1,3-dibromobenzene with a zinc chloride complex of pyridine, it can also be obtained by a coupling reaction in which 1,3-dibromobenzene is reacted with pyridylboronic acid or a pyridylboronic acid ester.

  In the above reaction formula (1), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

<Synthesis of 2-phenylanthracene-9,10-diboronic acid (or boronic ester)>
First, as shown in the following reaction formula (3), 2-phenyl-9,10-dibromoanthracene is obtained by brominating anthracene substituted with a phenyl group at the 2-position using an appropriate brominating agent. . Suitable brominating agents include bromine or N-brominated succinimide (NBS).

  Anthracene having a substituent at the 2-position (phenyl group in the above reaction formula (3)) is anthracene substituted at the 2-position with halogen or triflate and a boronic acid (or boronic ester of a group corresponding to the substituent). The anthracene having a substituent at the 2-position can be synthesized by Suzuki coupling. As another method, a synthesis method by Negishi coupling between anthracene substituted at the 2-position with halogen or triflate and a zinc complex of a group corresponding to the above substituent can be mentioned. Further, a synthesis method by Suzuki coupling of 2-anthraceneboronic acid (or boronate ester) and a group corresponding to the substituent substituted with halogen or triflate, and further, with 2-anthracene zinc complex and halogen or triflate A synthesis method by Negishi coupling with a group corresponding to the substituted group is also included. It should be noted that anthracene having a substituent other than the 2-position is similarly synthesized by using a raw material in which the position of halogen, triflate, boronic acid (or boronic acid ester) or zinc complex substituted for anthracene is set to a desired position. can do. In addition, 9,10-dibromoanthracene, which is a raw material for synthesizing the compounds represented by the formulas (1-201) to (1-215), can be easily obtained as a commercial product.

  Next, as shown in the following reaction formula (4), 2-phenyl-9,10-dibromoanthracene is lithiated using an organolithium reagent, or converted into a Grignard reagent using magnesium or an organomagnesium reagent. 2-phenylanthracene-9,10-diboronic acid ester can be synthesized by reacting with trimethyl acid, triethyl borate or triisopropyl borate. Furthermore, 2-phenylanthracene-9,10-diboronic acid can be synthesized by hydrolyzing the 2-phenylanthracene-9,10-diboronic acid ester in the following reaction formula (5).

  In the above reaction formula (4), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Further, as shown in the following reaction formula (6), 2-phenyl-9,10-dibromoanthracene is lithiated using an organolithium reagent, or converted into a Grignard reagent using magnesium or an organomagnesium reagent, and bis ( Other 2-phenylanthracene-9,10-diboronic acid esters can be synthesized by reacting with pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Further, as shown in the following reaction formula (7), 2-phenyl-9,10-dibromoanthracene and bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane A similar 2-phenylanthracene-9,10-diboronic acid ester can be synthesized by a coupling reaction using a palladium catalyst and a base.

  In the reaction formula (6), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  In the above reaction formula (4), (6) or (7), chloride, iodide or triflate may be used in place of bromide such as 2-phenyl-9,10-dibromoanthracene. Can be synthesized.

<Synthesis of Anthracene Derivative Compound According to the Present Invention by Suzuki Coupling Reaction>
Finally, as shown in the following reaction formula (8), 2-phenylanthracene-9,10-diboronic acid or 2-phenylanthracene-9,10-diboronic acid ester synthesized as described above is added to 2 The anthracene derivative compound according to the present invention can be synthesized by reacting double moles of 3-pyridyl-1-bromobenzene in the presence of a palladium catalyst and a base.

  In addition, as shown in the following reaction formula (9), 2-phenyl-9,10-dibromoanthracene is reacted with a 2-fold mole of boronic acid or boronic acid ester of pyridylbenzene in the presence of a palladium catalyst and a base. Thus, the anthracene derivative compound according to the present invention can be synthesized. The boronic acid or boronic acid ester of pyridylbenzene can be synthesized from 3-pyridyl-1-bromobenzene by a method according to the above reaction formulas (4) to (7).

Specific examples of the palladium catalyst used in the Suzuki coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0), tris ( Dibenzylideneacetone) dipalladium (0) chloroform complex or bis (dibenzylideneacetone) palladium (0).

  In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1′-bis (di-t-butylphos Fino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, or An example is 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl.

  Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphoric acid. Examples include tripotassium or potassium fluoride.

  Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4- Examples include dioxane, methanol, ethanol, cyclopentyl methyl ether, and isopropyl alcohol. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

<Method for Synthesizing Compound Represented by General Formula (1) (Part 2)>
<Synthesis of 2-phenylanthracene-9,10-dizinc complex>
First, as shown in the following reaction formula (10), 2-phenyl-9,10-dibromoanthracene is lithiated using an organolithium reagent, or converted into a Grignard reagent using magnesium or an organomagnesium reagent. Alternatively, a 2-phenylanthracene-9,10-dizinc complex can be synthesized by reacting with zinc chloride tetramethylethylenediamine complex (ZnCl ₂ · TMEDA).

  In the above reaction formula (10), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. In addition, it can synthesize | combine similarly even if it uses a chloride or iodide instead of bromides like 2-phenyl-9,10-dibromoanthracene. In addition, the case where an anthracene derivative having a substituent other than the 2-position is desired or that an unsubstituted anthracene may be used as a raw material is as described in the column of the Suzuki coupling reaction.

<Synthesis of anthracene derivative compound according to the present invention by Negishi coupling reaction>
Finally, as shown in the following reaction formula (11), 2-phenylanthracene-9,10-dizinc complex synthesized as described above was added with 2-fold mole of 3-pyridyl-1-bromobenzene as palladium. By reacting in the presence of a catalyst, the anthracene derivative compound according to the present invention can be synthesized.

  In addition, as shown in the following reaction formula (12), 2-phenyl-9,10-dibromoanthracene was synthesized from 3-pyridyl-1-bromobenzene by a method according to the above reaction formula (10). The anthracene derivative compound according to the present invention can be synthesized by reacting a molar 3-pyridylbenzene zinc complex in the presence of a palladium catalyst.

Specific examples of the palladium catalyst used in the Negishi coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0), tris ( Dibenzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphino) palladium (0), or (1,1′-bis (diphenylphosphino) Ferrocene) dichloropalladium (II).

  Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, cyclopentyl methyl ether or 1,4-dioxane. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

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

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

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

  Not all of the above-described layers are necessary, and the minimum structural unit is composed of the anode 102, the light-emitting layer 105, the electron transport layer 106 and / or the electron injection layer 107 and the cathode 108. The hole transport layer 104 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. As for the material of the glass, non-alkali glass is preferred because it is better that there are fewer ions eluted from the glass, but soda-lime glass with a barrier coat such as SiO ₂ is also available on the market. 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 100 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-allylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino group in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1, Triphenylamine derivatives such as '-diamine, 4,4', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, stilbene derivatives, phthalocyanine derivatives (metal free, copper phthalocyanine Etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, heterocyclic compounds such as oxadiazole derivatives, porphyrin derivatives, polysilanes, etc. In polymer systems, polycarbonates and styrene derivatives having the aforementioned monomers in the side chain Polyvinylcarbazole, polysilane, and the like are preferable, but the compound is not particularly limited as long as it is a compound that forms a thin film necessary for manufacturing a light-emitting element, can inject holes from the anode, and can 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 high emission (fluorescence and / or phosphorescence) efficiency.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting 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 of the entire light emitting material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight. .

  The amount of the dopant material used varies depending on the type of the dopant material, and may be determined according to the characteristics of the dopant material (for example, if the amount used is too large, there is a risk of concentration quenching). The standard of the amount of the 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 light emitting material.

  The light emitting material of the light emitting element according to the present embodiment may be either fluorescent or phosphorescent.

  The host material is not particularly limited, but has previously been known as a light emitter, such as fused ring derivatives such as anthracene and pyrene, metal chelated oxinoid compounds such as tris (8-quinolinolato) aluminum, bis Bisstyryl derivatives such as styryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, pyrrolopyrrole In derivatives, fluorene derivatives, benzofluorene derivatives, and polymer systems, polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives are preferably used.

  In addition, as a host material, 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.

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

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

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

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

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.
Also, 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 2000-34234 A, JP 2001-267075 A, JP 2001-217077 A 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.

  Examples of the amine-containing styryl derivative 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-dimethylfluorene , 4,4'-bis ( -Ethyl-3-carbazovinylene) -biphenyl, 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl, etc. JP-A 2003-347056 and JP-A 2001-307884 Amine-containing styryl derivatives described in the above may be used.

Examples of the aromatic amine derivative include N, N, N, N-tetraphenylanthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, and 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-9- (6-diphenylamino-2-naphthyl) anthracene, [4- (4-diphenyl) Amino-phenyl) naphthalen-1-yl] -diphenylamine, [4- (4-diphenylamino-phenyl) na Talen-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-diphenyl Aminonaphthalen-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.
JP-A-2005-126399, JP-A-2005-097283, JP-A-2002-234892, JP-A-2001-220577, JP-A-2001-081090, and JP-A-2001-052869 Alternatively, pyran derivatives described in the above may be used.

Examples of the iridium complex include Ir (ppy) _{3 described} below.
Further, the iridium complexes described in JP-A-2006-089398, JP-A-2006-080419, JP-A-2005-298483, JP-A-2005-097263, JP-A-2004-111379, etc. It may be used.

Examples of the platinum complex include the following PtOEP.
Further, platinum complexes described in JP-A-2006-190718, JP-A-2006-128634, JP-A-2006-093542, JP-A-2004-335122, JP-A-2004-331508, etc. It 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 represented by the above general formula (1) can be used. Among these, compounds represented by the above formula (1-1) to formula (1-48) are preferable, and the above formula (1-1) to formula (1-30) and formula (1-37) to formula (1) -42) is more preferred, the above formula (1-1), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1) A compound represented by 1-12), formula (1-27), formula (1-30) or formula (1-42) is particularly preferred.
The content of the compound represented by the general formula (1) in the electron transport layer 106 or the electron injection layer 107 differs depending on the type of the compound and may be determined according to the characteristics of the compound. The standard of the content of the compound represented by the general formula (1) is preferably 1 to 100% by weight, more preferably 10 to 100% by weight of the whole electron transport layer material (or electron injection layer material). % By weight, more preferably 50 to 100% by weight, and particularly preferably 80 to 100% by weight. When the compound represented by the general formula (1) is not used alone (100% by weight), other materials described in detail below may be mixed.

  Other materials for forming the electron transport layer or electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and known materials used for electron injection layers and electron transport layers of organic electroluminescent devices. Any of these compounds can be selected and 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. Among them, anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene, styryl aromatic ring derivatives such as 4,4′-bis (diphenylethenyl) biphenyl, 4,4′-bis (N-carbazolyl) biphenyl A carbazole derivative such as 1,3,5-tris (N-carbazolyl) benzene is preferably used from the viewpoint of durability.

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

  In addition, a metal complex having an electron-accepting nitrogen can be used, for example, a hydroxyazole complex such as a quinolinol-based metal complex or a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, or a benzoquinoline metal complex. can give.

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

  Among the materials described above, quinolinol 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 Al, Ga, Be, or Zn, and n is an integer of 2 or 3.

  Specific examples of the quinolinol-based metal complex include 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- Methyl phenolate) alumini Bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) 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-t-butylphenolate) alumini Bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolato) aluminum, bis (2 -Methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolato) aluminum, bis (2- Methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolato) aluminum Bis (2,4-dimethyl-8-quinolinolate) (3-phenylphenola) G) Aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) 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.

The bipyridine derivative is a compound represented by the following general formula (E-2).
In the formula, G represents a simple bond or an n-valent linking group, and n is an integer of 2 to 8. Carbon atoms that are not used for bonding of pyridine-pyridine or pyridine-G may be substituted.

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

  Specific examples of the pyridine derivative include 2,5-bis (2,2′-bipyridyl-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Bipyridyl-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-bipyridyl-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-bipyridyl-5-yl) -1,1-dimethyl-3,4-dimesitylsilole 9,10-di (2,2′-bipyridyl-6- Yl) anthracene, 9,10-di (2,2′-bipyridyl-5-yl) anthracene, 9,10-di (2,3′-bipyridyl-6-yl) anthracene, 9,10-di (2, 3'-bipyridyl-5-yl) anthracene, 9,10-di (2,3 -Bipyridyl-6-yl) -2-phenylanthracene, 9,10-di (2,3'-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridyl-6) -Yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (2,4'-bipyridyl-6-yl)- 2-Phenylanthracene, 9,10-di (2,4′-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (3,4′-bipyridyl-6-yl) -2-phenylanthracene 9,10-di (3,4'-bipyridyl-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2'-bipyridyl-6-yl) thiophene, 3, , 4-Diphenyl 2,5-di (2,3′-bipyridyl-5-yl) thiophene, 6′6 ″ -di (2-pyridyl) 2,2 ′: 4 ′, 4 ″: 2 ″, 2 ″ ′-quater Examples include pyridine.

The 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. Examples of G in the general formula (E-3-2) include the same ones as described in the bipyridine derivative column.

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

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 preferred. Specific examples include 9- [4- (4-Dimesitylborylnaphthalen-1-yl) phenyl] carbazole, 9- [4- (4-Dimesitylborylnaphthalen-1-yl) naphthalen-1-yl. Carbazole and the like.
In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. At least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and R ²¹ and R ²² are each independently Each independently is at least one of a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group, and X ¹ is , An optionally substituted arylene group having 20 or less carbon atoms, n is each independently an integer of 0 to 3, and m is each independently an integer of 0 to 4.

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

In the 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 above general formula (E-4), the compound represented by the following general formula (E-4-3), and further the following general formula (E-4-3-1) or (E-4 The compound represented by -3-2) is preferable.
In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, a substituted silyl group, an optionally substituted nitrogen-containing heterocyclic group, or a cyano group. And at least one, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl group or an optionally substituted aryl group, and X ¹ is an optionally substituted carbon. It is an arylene group of several tens or less, Y ¹ is an optionally substituted aryl group having 14 or less carbon atoms, and n is each independently an integer of 0 to 3.

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 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 the like, and 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, for example, 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 life 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, magnesium, 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 substances 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, polysulfone, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin , Dispersed in solvent-soluble resins such as polyurethane resin, curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. To be possible.

<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 casting 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 intended crystal structure and association structure of the film, and the like. Deposition conditions generally include boat heating temperature of 50 to 400 ° C., vacuum degree of 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate of 0.01 to 50 nm / second, substrate temperature of −150 to + 300 ° C., and film thickness of 2 nm to 5 μm. It is preferable to set appropriately within the range.

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

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

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

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

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

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

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

  First, synthesis examples of the compounds used in Examples and physical property values of the compounds will be described below. The glass transition temperature (Tg) was measured using Diamond DSC manufactured by PerkinElmer (measurement conditions: cooling rate 200 ° C./min, temperature rising rate 10 ° C./min).

<Synthesis Example of Compound Represented by Formula (1-1)>
9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene (1.8 g), 3- (4-pyridyl) bromobenzene ( 1.8 g), tris (dibenzylideneacetone) dipalladium (0) (82 mg), tricyclohexylphosphine (73 mg), tripotassium phosphate (4.46 g), toluene (20 mL) were placed in a flask under an argon atmosphere. The mixture was stirred at reflux temperature for 9 hours. After completion of the heating, the reaction solution was cooled to room temperature and washed with water, followed by concentration under reduced pressure. The obtained crude product was purified by silica gel column chromatography (toluene-ethyl acetate), and the compound “9,10-bis (3- (4-pyridyl) phenyl)-represented by formula (1-1) — 2-phenylanthracene "(0.89 g) was obtained. The glass transition temperature (Tg) of the obtained compound was 123 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 8.7 (m, 4H), 7.9 to 7.7 (m, 10H), 7.7 to 7.5 (m, 9H), 7.4 to 7. 3 (m, 5H).

<Synthesis Example of Compound Represented by Formula (1-2)>
9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene (6.0 g), 3- (3-pyridyl) bromobenzene ( 6.1 g), tetrakis (triphenylphosphine) palladium (0) (0.69 g), toluene (20 ml), ethanol (8 mL), potassium carbonate aqueous solution (potassium carbonate 4.8 g-water 8 ml) were placed in a flask and argon was added. The mixture was stirred at reflux temperature for 13 hours under an atmosphere. After completion of the heating, the reaction solution was cooled to room temperature and washed with water, followed by concentration under reduced pressure. The obtained crude product was purified by silica gel column chromatography (toluene-ethyl acetate) to obtain a compound “9,10-bis (3- (3-pyridyl) phenyl)-represented by the formula (1-2) — 2-Phenylanthracene "(5.3 g) was obtained. The obtained compound had a glass transition temperature (Tg) of 113 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 9.0 (m, 2H), 8.6 (m, 2H), 8.0 (m, 3H), 7.9 to 7.8 (m, 9H), 7 .7-7.5 (m, 5H), 7.4-7.3 (m, 7H).

<Synthesis Example of Compound Represented by Formula (1-3)>
9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene (3.1 g), 4- (3-pyridyl) bromobenzene ( 3.0 g), tetrakis (triphenylphosphine) palladium (0) (0.35 g), toluene (20 ml), ethanol (2 mL), potassium carbonate aqueous solution (potassium carbonate 1.28 g—water 2 ml) were placed in a flask and argon was added. The mixture was stirred at reflux temperature for 25 hours under an atmosphere. After completion of heating, the reaction solution was cooled to room temperature and filtered. The obtained crude product was washed with water and methanol and then recrystallized with chlorobenzene to give a compound “9,10-bis (4- (3-pyridyl) phenyl)-represented by the formula (1-3) 2-Phenylanthracene "(1.9 g) was obtained. The glass transition temperature (Tg) of the obtained compound was 128 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 9.1 (d, 2H), 8.7 (m, 2H), 8.1 (d, 2H), 8.0 (s, 1H), 7.9 (d , 5H), 7.8 (m, 2H), 7.7 to 7.6 (m, 5H), 7.6 (d, 2H), 7.5 to 7.3 (m, 7H).

<Synthesis Example of Compound Represented by Formula (1-4)>
9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene (5.0 g), 4- (2-pyridyl) bromobenzene ( 5.0 g), tetrakis (triphenylphosphine) palladium (0) (0.57 g), toluene (20 ml), ethanol (7 mL), aqueous potassium carbonate (4.2 g potassium carbonate-7 ml water) in a flask, The mixture was stirred at reflux temperature for 14.5 hours under atmosphere. After completion of heating, the reaction solution was cooled to room temperature and filtered. The obtained crude product was washed with water and methanol, and then recrystallized with chlorobenzene to give the compound “9,10-bis (4- (2-pyridyl) phenyl)-represented by the formula (1-4)”. 2-Phenylanthracene "(3.5 g) was obtained. The glass transition temperature (Tg) of the obtained compound was 134 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 8.8 (d, 2H), 8.3 (d, 4H), 8.0 to 7.7 (m, 8H), 7.6 to 7.4 (m, 5H), 7.4 (d, 2H) 7.4 to 7.3 (m, 7H).

<Synthesis Example of Compound Represented by Formula (1-6)>
9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene (4.0 g), 4- (4-pyridyl) bromobenzene ( 4.4 g), tris (dibenzylideneacetone) dipalladium (0) (91 mg), tricyclohexylphosphine (89 mg), tripotassium phosphate (6.7 g) and 1,2,4-trimethylbenzene (15 mL). And stirred at 170 ° C. for 23 hours under an argon atmosphere. After completion of heating, the reaction solution was cooled to room temperature and filtered. The obtained solid was washed with water and methanol and then subjected to Soxhlet extraction with chlorobenzene. The extract was concentrated with an evaporator, and the concentrate was recrystallized with chlorobenzene to obtain a compound “9,10-bis (4- (4-pyridyl) phenyl) -2-phenylanthracene represented by the formula (1-6). (1.5 g) was obtained. The glass transition temperature (Tg) of the obtained compound was 145 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.3 (t, 1H), 7.4 (m, 4H), 7.5 (d, 2H), 7.65 (m, 5H), 7.7 (d , 4H), 7.75 (m, 2H), 7.85 (d, 1H), 7.9 (m, 5H), 8.8 (m, 4H).

<Synthesis Example of Compound Represented by Formula (1-12)>
First, in order to synthesize 2- (biphenyl-2-yl) anthracene, 2-biphenylboronic acid (9.2 g), 2-bromoanthracene (10.0 g), Pd (PPh ₃ ) ₄ (1.4 g) Sodium carbonate (8.3 g), toluene (100 ml), ethanol (20 ml) and water (20 ml) were placed in a flask and stirred at reflux temperature for 5 hours under an argon stream. After completion of heating, the reaction solution was cooled to room temperature, and the reaction solution was extracted with toluene. This toluene solution was concentrated by an evaporator, and the concentrate was purified by silica gel column chromatography (toluene). Furthermore, it recrystallized with a heptane / toluene mixed solution (volume ratio 10/1) to obtain 2- (biphenyl-2-yl) anthracene (11.3 g).

  Next, in order to synthesize 2- (biphenyl-2-yl) -9,10-dibromoanthracene, 2- (biphenyl-2-yl) anthracene (11.3 g) obtained as described above, Dichloromethane (200 ml) was placed in the flask and stirred at room temperature. Under a nitrogen atmosphere, a dichloromethane solution (40 ml) containing bromine (12.0 g) was added dropwise to this solution, and the mixture was stirred at room temperature for 1 hour. After stirring, an aqueous sodium thiosulfate solution was added and extracted with toluene. This toluene solution was concentrated with an evaporator and dissolved again in toluene. Then, heptane was gradually added to obtain precipitated 2- (biphenyl-2-yl) -9,10-dibromoanthracene crystals (12.7 g). .

Finally, in order to synthesize the compound “2- (biphenyl-2-yl) -9,10-bis (4- (2-pyridyl) phenyl) anthracene” represented by the formula (1-12), 2- (biphenyl-2-yl) -9,10-dibromoanthracene (4.9 g) thus obtained and 2- (4- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolanyl) phenyl) pyridine (5.0 g), Pd (PPh ₃ ) ₄ (935 mg), tripotassium phosphate (6.9 g), toluene (15 ml), ethanol (3 ml) and water (3 ml) ) Was placed in a flask and stirred at reflux temperature for 16 hours under a stream of argon. After the heating, the reaction solution was cooled to room temperature, water and toluene were added, and a toluene layer was obtained by analytical operation. This toluene solution was concentrated by an evaporator, and the concentrate was purified by activated alumina column chromatography (toluene). Further, after washing with ethyl acetate, the compound “2- (biphenyl-2-yl) -9,10-bis (4- (2-pyridyl) phenyl) anthracene” represented by the formula (1-12) (1. 8 g) was obtained. The glass transition temperature (Tg) of the obtained compound was 143 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.1 (m, 2H), 7.15 to 7.4 (m, 13H), 7.45 (m, 1H), 7.55 (m, 1H), 7 .6 (d, 2H), 7.65 (d, 1H), 7.7 to 7.8 (m, 2H), 7.8 to 7.9 (m, 4H), 8.1 (d, 2H) ), 8.25 (d, 2H), 8.8 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-27)>
9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-m-terphenyl-5′-ylanthracene (5.0 g), 3- (2-pyridyl) bromobenzene (4.3 g), tris (dibenzylideneacetone) dipalladium (0) (87 mg), tricyclohexylphosphine (85 mg), tripotassium phosphate (9.7 g) and 1,2,4 -Trimethylbenzene (10 ml) was placed in a flask and stirred at 170 ° C for 3.5 hours under an argon atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, EDTA · 4Na water was added, and the mixture was extracted with ethyl acetate. The ethyl acetate solution was washed with water and concentrated with an evaporator. The concentrate was purified by activated alumina column chromatography (toluene-ethyl acetate) and then activated carbon column chromatography (toluene), and the compound “9,10-bis (3- (2 -Pyridyl) phenyl) -2- (m-terphenyl-5′-yl) anthracene ”(3.5 g) was obtained. The glass transition temperature (Tg) of the obtained compound was 137 ° C. The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.2 (m, 2H), 7.35 (m, 4H), 7.4 (t, 4H), 7.6 (m, 6H), 7.7-7 .85 (m, 12H), 7.9 (d, 1H), 8.1 (m, 1H), 8.15 (m, 1H), 8.2 to 8.3 (m, 3H), 8. 7 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-30)>
First, in order to synthesize 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) phenyl) pyridine, 4- (2-pyridyl) bromobenzene ( 11.4 g), bispinacolato diboron (14.8 g), (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II) (1.19 g), potassium acetate (14.3 g) and cyclopentyl Methyl ether (50 ml) was placed in a flask and stirred at reflux temperature for 1 hour under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, EDTA · 4Na water was added, and the mixture was extracted with toluene. The toluene solution was washed with water and concentrated with an evaporator. The concentrate was purified by activated carbon column chromatography (toluene) to give 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) phenyl) pyridine (11. 8 g) was obtained.

Next, in order to synthesize 9,10-bis (4- (2-pyridyl) phenyl) -2- (m-terphenyl-5′-yl) anthracene, the 9,10 obtained as described above was used. -Dibromo-2-m-terphenyl-5'-ylanthracene (3.3 g) and 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) ) Phenyl) pyridine (4.0 g), Pd (PPh ₃ ) ₄ (340 mg), tripotassium phosphate (5.0 g), toluene (10 ml), ethanol (2 ml) and water (2 ml) were placed in a flask. The mixture was stirred at reflux temperature for 13 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and the precipitated crystals were separated by filtration. The obtained crystal was washed with water and then with methanol, and then recrystallized with toluene to obtain a compound “9,10-bis (4- (2-pyridyl) phenyl) -2 represented by the formula (1-30). -(M-Terphenyl-5'-yl) anthracene (0.97 g) was obtained, and the glass transition temperature (Tg) of the obtained compound was 140 ° C. The structure of the compound obtained by NMR measurement was determined. confirmed.
¹ H-NMR (CDCl ₃ ): 7.26-7.45 (m, 10H), 7.6-7.95 (m, 19H), 8.17 (m, 1H), 8.27 (t, 4H), 8.75-8.8 (m, 4H).

<Synthesis Example of Compound Represented by Formula (1-42)>
First, in order to synthesize 2- (naphthalen-1-yl) anthracene, 1-naphthaleneboronic acid (10.0 g), 2-bromoanthracene (12.5), Pd (PPh ₃ ) ₄ (1.1 g) Sodium carbonate (10.3 g), toluene (100 ml), ethanol (20 ml) and water (20 ml) were placed in a flask and stirred at reflux temperature for 5.5 hours under a stream of argon. After heating, the reaction solution was cooled to room temperature, and the reaction solution was extracted with toluene. The toluene solution was concentrated with an evaporator, and the concentrate was purified by silica gel column chromatography (toluene). Furthermore, recrystallization was performed with a tetrahydrofuran / ethyl acetate mixed solution (volume ratio 5/1) to obtain 2- (naphthalen-1-yl) anthracene (11.6 g).

  Next, in order to synthesize 9,10-dibromo-2- (naphthalen-1-yl) anthracene, 2- (naphthalen-1-yl) anthracene (4.3 g) obtained as described above, Dichloromethane (100 ml) was placed in the flask and stirred at room temperature. Under a nitrogen atmosphere, a dichloromethane solution (20 ml) containing bromine (5.0 g) was added dropwise to this solution and stirred at room temperature for 2 hours. After stirring, an aqueous sodium thiosulfate solution was added, and the mixture was extracted with chloroform. The chloroform solution was concentrated with an evaporator to obtain 9,10-dibromo-2- (naphthalen-1-yl) anthracene (4.7 g).

Finally, in order to synthesize the compound “9,10-bis (4- (2-pyridyl) phenyl) -2- (naphthalen-1-yl) anthracene” represented by the formula (1-42), Thus obtained 9,10-dibromo-2- (naphthalen-1-yl) anthracene (2.6 g), 2- (4- (4,4,5,5-tetramethyl-1,3,2) -Dioxaborolanyl) phenyl) pyridine (4.0 g), Pd (PPh ₃ ) ₄ (329 mg), tripotassium phosphate (4.8 g), toluene (20 ml), ethanol (4 ml) and water (4 ml) Was stirred at reflux temperature for 32.5 hours under an argon stream. After completion of heating, the reaction solution was cooled to room temperature, and the precipitated crystals were separated by filtration. The crystals were dissolved in chlorobenzene, and salts generated by the reaction were removed by filtration. The filtrate was concentrated by an evaporator, and the concentrate was purified by activated alumina column chromatography (toluene). Further, the resultant was washed with ethyl acetate and then recrystallized with chlorobenzene, and the compound represented by the formula (1-42) “9,10-bis (4- (2-pyridyl) phenyl) -2- (naphthalen-1-yl)” Anthracene (1.9 g) was obtained, and the glass transition temperature (Tg) of the obtained compound was 147 ° C. The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 7.25 (m, 1H), 7.3 (m, 1H), 7.35 to 7.5 (m, 6H), 7.55 (d, 1H), 7 .65 (d, 2H), 7.7 (d, 2H), 7.75-7.95 (m, 11H), 8.17 (d, 2H), 8.3 (d, 2H), 8. 7 (m, 1H), 8.8 (m, 1H).

  By appropriately changing the raw material compound, another phenylpyridine derivative compound of the present invention can be synthesized by a method according to the synthesis example described above.

  Hereinafter, each example will be shown to describe the present invention in more detail, but the present invention is not limited thereto.

The electroluminescent elements according to Examples 1 to 4 and Comparative Examples 1 and 2 were manufactured, and the drive start voltage (V) and the luminance after the elapse of 80 hours (cd / m ² ) were measured in the constant current drive test, respectively. It was. Hereinafter, examples and comparative examples will be described in detail.

Table 1 below shows the material structure of each layer in the electroluminescent elements according to Examples 1 to 4 and Comparative Examples 1 and 2.

  In Table 1, “CuPc” is copper phthalocyanine, “NPD” is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, and compound (A) is 9-phenyl-10- [6 -(1,1 '; 3,1 ") terphenyl-5'-yl] naphthalen-2-yl] anthracene, compound (B) is N, N, N', N'-tetra (4-biphenylyl) -4,4'-diaminostilbene, compound (C) is 2-biphenyl-2-yl-9,10-bis [4- (2,6-diphenylpyridyl) phenyl] anthracene, and "Alq3" is tris (8- Quinolinol) aluminum, each having the following chemical structure:

<Example 1>
A 26 mm × 28 mm × 0.7 mm glass substrate (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 Vacuum Kiko Co., Ltd.), and a molybdenum vapor deposition boat containing CuPc, a molybdenum vapor deposition boat containing NPD, and a compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound represented by formula (1-1), molybdenum vapor deposition containing lithium fluoride A boat and a tungsten evaporation boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, the vapor deposition boat containing CuPc was heated to form a hole injection layer by vapor deposition to a film thickness of 50 nm, and then NPD entered. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound represented by the formula (1-1) was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the vapor deposition boat containing lithium fluoride is heated to deposit at a deposition rate of 0.003 to 0.1 nm / second so that the film thickness becomes 0.5 nm, and then the vapor deposition boat containing aluminum is heated. The cathode was formed by vapor deposition at a deposition rate of 0.01 to 10 nm / second so that the film thickness was 100 nm, and an organic electroluminescent element was obtained.

When a direct current voltage was applied using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, blue light emission with a wavelength of about 455 nm was obtained. In addition, a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 5.27 V, and the luminance after 80 hours was 1799 cd / m ² .

<Example 2>
An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-1) was replaced with the compound represented by the formula (1-2). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.85 V, and the luminance after 80 hours was 1677 cd / m ² .

<Example 3>
An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-1) was changed to the compound represented by the formula (1-3). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 5.09 V, and the luminance after 80 hours was 1676 cd / m ² .

<Example 4>
An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-1) was changed to the compound represented by the formula (1-4). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test starting voltage was 5.21 V, and the luminance after 80 hours was 1656 cd / m ² .

<Comparative Example 1>
An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-1) was changed to the compound (C). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test starting voltage was 6.84 V, and the luminance after 80 hours was 1664 cd / m ² .

<Comparative example 2>
An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-1) was changed to Alq3. A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 6.58 V, and the luminance after 80 hours was 1562 cd / m ² .

The above results are summarized in Table 2.

The electroluminescent elements according to Examples 5 to 9 and Comparative Examples 3 and 4 were prepared, and the driving start voltage (V) and the luminance after 80 hours (cd / m ² ) were measured in the constant current driving test, respectively. It was. Hereinafter, examples and comparative examples will be described in detail.

Table 3 below shows the material configuration of each layer in the electroluminescent elements according to Examples 5 to 9 and Comparative Examples 3 and 4 thus manufactured.

In Table 3, “CuPc”, “NPD”, compound (A) and “Alq3” are the same as in Table 1, and compound (D) is N ⁵ , N ⁵ , N ⁹ , N ⁹ -7,7-hexa. Phenyl-7H-benzo [C] fluorene-5,9-diamine, Compound (E) is 9,10-bis (3- (2,6-diphenylpyridin-4-yl) phenyl) anthracene, Has a chemical structure.

<Example 5>
A 26 mm × 28 mm × 0.7 mm glass substrate (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 Vacuum Kiko Co., Ltd.), and a molybdenum vapor deposition boat containing CuPc, a molybdenum vapor deposition boat containing NPD, and a compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (D), molybdenum vapor deposition boat containing compound represented by formula (1-6), molybdenum vapor deposition containing lithium fluoride A boat and a tungsten evaporation boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing CuPc was heated to deposit to a film thickness of 100 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (D) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (D) was approximately 95 to 5. Next, the evaporation boat containing the compound represented by the formula (1-6) was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the vapor deposition boat containing lithium fluoride is heated to deposit at a deposition rate of 0.003 to 0.1 nm / second so that the film thickness becomes 0.5 nm, and then the vapor deposition boat containing aluminum is heated. The cathode was formed by vapor deposition at a deposition rate of 0.01 to 10 nm / second so that the film thickness was 100 nm, and an organic electroluminescent element was obtained.

When a direct current voltage was applied using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. In addition, a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 4.87 V, and the luminance after 80 hours was 1595 cd / m ² .

<Example 6>
An organic EL device was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-6) was changed to the compound represented by the formula (1-12). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.63 V, and the luminance after 80 hours was 1366 cd / m ² .

<Example 7>
An organic EL device was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-6) was changed to the compound represented by the formula (1-27). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 4.94 V, and the luminance after the lapse of 80 hours was 1261 cd / m ² .

<Example 8>
An organic EL device was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-6) was changed to the compound represented by the formula (1-30). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test starting voltage was 4.73 V, and the luminance after 80 hours was 1366 cd / m ² .

<Example 9>
An organic EL device was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-6) was changed to the compound represented by the formula (1-42). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 4.59 V, and the luminance after 80 hours was 1303 cd / m ² .

<Comparative Example 3>
An organic EL device was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-6) was changed to the compound (E). A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test starting voltage was 7.12 V, and the luminance after the lapse of 80 hours was 1609 cd / m ² .

<Comparative example 4>
An organic EL device was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-6) was changed to Alq3. A constant current driving test was carried out using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 6.91 V, and the luminance after the elapse of 80 hours was 1791 cd / m ² .

The above results are summarized in Table 4.

  According to a preferred aspect of the present invention, an organic electroluminescent element that improves the characteristics of the driving voltage and has an excellent balance between the lifetime and stability of the element, a display device including the organic electroluminescent device, and a lighting device including the organic electroluminescent device. Can be provided.

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

Explanation of symbols

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 (11)

A compound represented by the following general formula (1).
In formula (1),
R ¹ is hydrogen, alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons or aryl having 6 to 20 carbons;
R ² , R ³ and R ⁴ are each independently hydrogen, alkyl having 1 to 12 carbons or cycloalkyl having 3 to 12 carbons, and
Ar is each independently a group represented by any of the following formulas Ar1, Formula Ar2, Formula Ar3, Formula Ar4, Formula Ar5, or Formula Ar6.
R ¹ is alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons or aryl having 6 to 20 carbons, R ² , R ³ and R ⁴ are hydrogen, and
Ar is a group represented by any one of formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6,
The compound according to claim 1. R ¹ is aryl having 6 to 20 carbon atoms,
R ² , R ³ and R ⁴ are hydrogen and
Ar is a group represented by any one of formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6,
The compound according to claim 1. R ¹ is phenyl, biphenylyl, terphenylyl, or naphthyl, R ² , R ^3, and R ⁴ are hydrogen, and
Ar is a group represented by any one of formula Ar1, formula Ar2, formula Ar3, formula Ar4, formula Ar5 or formula Ar6,
The compound according to claim 1. Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), Formula (1-6), Formula (1-12), Formula (1-27), The compound according to claim 1, which is represented by formula (1-30) or formula (1-42).
  The electron transport material containing the compound in any one of Claims 1-5.   An electron transport containing an electron transport material according to claim 6, disposed between a pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and the cathode and the light emitting layer. An organic electroluminescent device comprising a layer and / or an electron injection layer.   The organic material according to claim 7, wherein at least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. Electroluminescent device.   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, an 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 8.   The display apparatus provided with the organic electroluminescent element in any one of Claims 7-9.   The illuminating device provided with the organic electroluminescent element in any one of Claims 7-9.