KR20120029343A - Pyridylphenyl substituted anthracene compound and organic electroluminescence element - Google Patents

Abstract

PURPOSE: A pyridylphenyl-substituted anthracene compound is provided to improve the life time of light emitting diode, and offering an organic electroluminescent device even having excellent balance with driving voltage. CONSTITUTION: A pyridylphenyl-substituted anthracene compound contains a compound in chemical formula 1. In chemical formula 1, Ar is C10-24 aryl. The aryl is substituted or non-substituted C1-12 alkyl, C3-12 cycloalkyl or c6-20 aryl, and is connected by 4-pyridyl group to the 3 or 4 location of phenyl. In chemical formula 1, at least one hydrogen is able to be substituted to deuterium. An organic electroluminescence device comprises a pair of electrodes consisting of a positive electrode and a negative electrode, a light emitting layer arranged between the pair of electrodes, and an electron transport layer and/or an electron injection layer arranged between the negative electrode and an electroluminescent layer thereof, and containing above compound.

Description

Pyridylphenyl substituted anthracene compound and organic electroluminescent device {PYRIDYLPHENYL SUBSTITUTED ANTHRACENE COMPOUND AND ORGANIC ELECTROLUMINESCENCE ELEMENT}

The present invention relates to pyridylphenyl substituted anthracene compounds, more particularly 9,10-bis (4- (pyridin-4-yl) phenylanthracene compound or 9,10-bis (3- (pyridin-4-yl) phenylanthracene A compound and the organic electroluminescent element, display apparatus, and lighting device using the same are provided.

BACKGROUND ART Conventionally, display devices using light emitting elements that emit electroluminescence can be reduced in power consumption and reduced in thickness, and various studies have been conducted, and organic electroluminescent elements made of organic materials are actively active in light weight and easy in size. Has been reviewed. In particular, the development of organic materials having luminescent properties including blue, which is one of the three primary colors of light, and the development of organic materials having electron transport ability (possibly to be a semiconductor or a superconductor) such as holes and electrons, are described in Regardless of their molecular weight, they have been actively studied to date.

For example, the synthesis | combining method of the compound which has a pyridylphenyl structure in a molecule | numerator, and the organic electroluminescent element which used this compound for the organic compound layer are reported (Unexamined-Japanese-Patent No. 2003-282270 (patent document 1)). In patent document 1, the organic electroluminescent element which used the compound which has a pyridyl phenyl structure in a molecule especially as an electron carrying material is reported. Moreover, the organic electroluminescent element using the compound in which the pyridylphenyl group was substituted by the center skeleton of anthracene is also reported (Japanese Unexamined-Japanese-Patent No. 2009-173642 (patent document 2)).

Japanese Unexamined Patent Publication No. 2003-282270 Japanese Unexamined Patent Publication No. 2009-173642

As mentioned above, although the electron transport material of the compound which has a pyridylphenyl structure in a molecule | numerator is known several, these well-known materials are light emission generally required for an electron transport material (material of an electron transport layer or an electron injection layer). In view of the long life of the device, it did not have sufficient characteristics. In such a situation, development of an electron transport material which can improve the element lifetime of a light emitting element is calculated | required. In particular, the blue light emitting device has not been obtained an electron transport material having superior characteristics as compared with the red or green light emitting device, and development of an electron transport material suitable for the long life of the blue light emitting device is required.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it turned out that organic electroluminescent element provided with the organic layer containing the compound represented by following General formula (1) as an electron carrying material is especially excellent in the lifetime characteristic of an element. The electroluminescent element was found and the present invention was completed.

[1] An electron transporting material containing a compound represented by the following General Formula (1).

[Formula 4]

In formula (1), Ar is carbon number 10? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, the 4-pyridyl group may be connected together to the 3 or 4 position of phenyl, and at least 1 hydrogen in the compound represented by Formula (1) may be substituted by deuterium.

[2] An electron transporting material containing a compound represented by the following General Formula (1-1).

[Chemical Formula 5]

In formula (1-1), Ar is C10? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, and at least 1 hydrogen in the compound represented by Formula (1-1) may be substituted by deuterium.

[3] An electron transporting material containing a compound represented by the following General Formula (1-2).

[Formula 6]

In formula (1-2), Ar is carbon number 10? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, and at least 1 hydrogen in the compound represented by Formula (1-2) may be substituted by deuterium.

[4] Ar is biphenylyl, terphenylyl or naphthyl, and the naphthyl may be substituted with phenyl; The electron transport material in any one of [3].

[5] Ar is 3-biphenylyl, 4-biphenylyl, m-terphenyl-5'-yl, 1-naphthyl or 2-naphthyl; The electron transport material in any one of [3].

[6] A pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and a cathode and the light emitting layer disposed between the above-mentioned [1]? The organic electroluminescent element which has an electron carrying layer and / or an electron injection layer containing the electron carrying material in any one of [5].

[7] At least one of the electron transport layer and the electron injection layer may further include at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. The organic electroluminescent element as described in said [6] containing.

[8] 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 oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, and a rare earth. [6] or [7] described in the above [6] or [7], containing at least one selected from the group consisting of oxides of metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. Organic electroluminescent device.

[9] above [6]? The display apparatus provided with the organic electroluminescent element in any one of [8].

[10] The above [6]? The illuminating device provided with the organic electroluminescent element in any one of [8].

According to a preferred aspect of the present invention, an organic electroluminescent device having a particularly long driving life can be obtained. Moreover, the preferable electron transport material of this invention is especially preferable for a blue light emitting element, and can manufacture the blue light emitting element which has an element lifetime comparable to a red or green light emitting element to this electron transport material. Moreover, by using this organic electroluminescent element, a high performance display device such as full color display can be obtained.

1 is a schematic cross-sectional view showing an organic electroluminescent element according to the present embodiment.

1. Compound represented by General Formula (1), Formula (1-1) and Formula (1-2)

Hereinafter, 9,10-bis (3- (pyridine) represented by 9,10-bis (4- (pyridin-4-yl) phenylanthracene compound represented by general formula (1-1) and general formula (1-2) The 4-yl) phenylanthracene compound is explained in full detail. Moreover, the structure represented by General formula (1) is a superposition which combined the structure of Formula (1-1) and Formula (1-2). In the pyridylphenyl group, in particular, the "4- (pyridin-4-yl) phenyl group" or "3- (pyridin-4-yl) phenyl group" is substituted at the 9 and 10 positions of the anthracene structure, Especially, it is a compound which substituted "an aryl group whose bulk is larger than a phenyl group" in the 2nd position of an anthracene structure, and is a compound which achieved the element life more excellent when used for organic electroluminescent element by selecting such a substituent.

Ar in Formula (1-1) or Formula (1-2) is a C10-C? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, and at least 1 hydrogen in the compound represented by Formula (1-1) or Formula (1-2) may be substituted by deuterium.

Ar phosphorus 10 carbon number? Aryl of 24 " 24 aryl is preferable, and especially C18? Preference is given to aryl of 24.

"10 carbon number? 24 aryl "is (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is condensed bicyclic aryl, and tricyclic aryl is Terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4 '-Yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic system Aryl, anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4 -, 9-) yl, penalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, condensed tetracyclic triphenylene- (1-, 2-) yl, pyren- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl, perylene- (1-, 2-, 3-) work etc. are mentioned.

Desirable "C10? Aryl "is biphenylyl, terphenylyl or naphthyl, more preferably m-terphenyl-5'-yl or 1-naphthyl.

The substituent of Ar is "carbon number 1? 12 alkyl "may be either a straight chain or a branched chain. That is, carbon number 1? Straight chain alkyl of 12 or 3? Branched chain alkyl of 12. More preferably, it is C1-C? Alkyl of 6 (branched chain alkyl of 3 to 6 carbon atoms), more preferably 1 to 6 carbon atoms. 4 alkyl (branched chain alkyl of 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentene, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, and the like, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s- Butyl or t-butyl is preferred, and methyl, ethyl or t-butyl is more preferred.

The substituent of Ar "carbon number 3? 12 cycloalkyl "may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

The substituent of Ar is "carbon number 6? Aryl of 20 " 12 aryl is preferable and carbon number 6? Particular preference is given to aryl of 10. As a specific example, in addition to a phenyl group, said "carbon number of 10? 24 aryl ", and are preferably phenyl, (2-, 3-, 4-) biphenylyl, (1-, 2-) naphthyl, and the like, and particularly preferably phenyl. to be.

When Ar has a substituent, the number of substituents is the number which can be substituted maximum, for example, Preferably it is 1? Three, more preferably 1? Two, more preferably one.

Specific examples of Ar (structure containing a substituent) include the following groups.

[Formula 7]

[Formula 8]

[Formula 9]

Moreover, all or part of the hydrogen atom in the anthracene skeleton, the hydrogen atom in the pyridylphenyl group, or the hydrogen atom in Ar which comprises the compound represented by General formula (1-1) and (1-2) Deuterium may be sufficient. When the compound is deuterated, it is preferable that the hydrogen atom in the pyridylphenyl group and the hydrogen atom in Ar are deuterated.

As a specific example of a compound represented by the said General formula (1-1), it is a following formula (1-1-1)? The compound represented by Formula (1-1-12) is mentioned. Among the following compounds, the following formula (1-1-2)? The compound represented by Formula (1-1-4), Formula (1-1-7), and Formula (1-1-10) is preferable.

[Formula 10]

As a specific example of a compound represented by following General formula (1-2), it is a following formula (1-2-1)? The compound represented by Formula (1-2-12) is mentioned. Among the following compounds, the following formula (1-2-1), formula (1-2-2), formula (1-2-4), formula (1-2-7) and formula (1-2-10) The compound represented is preferable.

[Formula 11]

2. Manufacturing method of compound represented by general formula (1-1) and (1-2)

Next, the manufacturing method of the compound of this invention is demonstrated. The compound of the present invention is basically a known synthetic method using a known compound, for example, a Suzuki coupling reaction or a Negishi coupling reaction (for example, "Metal-Catalyzed Cross-Coupling Reactions-Second, Completely"). Revised and Enlargcd Editon et al.). Moreover, it can synthesize | combine also by combining both reactions. The scheme which synthesize | combines the compound represented by General formula (1-1) and (1-2) by a Suzuki coupling reaction or a Negishi coupling reaction is illustrated below.

When preparing the compound of this invention, (1) the method which synthesize | combined the group which combined pyridyl (terminal group) and phenyl (intermediate group), and couple | bonds it with the 9, 10 position of anthracene, (2) 9, of anthracene A method of bonding a phenyl group to the 10 position and bonding a pyridyl group to the phenyl group is mentioned. However, in these methods, in the coupling | bonding of a phenyl group and a pyridyl group, and an anthracene and a phenyl group, basically, a halogen functional group or a trifluoromethanesulfonate functional group, a zinc chloride complex, or a coupling of boronic acid (boronic acid ester) Ring reactions can be used.

First, (1) the method which synthesize | combined the group which combined the pyridyl (terminal group) and phenyl (intermediate group), and demonstrates this method to couple to the 9, 10 position of anthracene. In addition, about (2) the method of couple | bonding a phenyl group to the 9, 10 position of anthracene, and a pyridinyl group to this phenyl group, with reference to the various coupling reactions demonstrated by (1) method, A phenyl group may be bonded to the 9 and 10 positions, and a pyridyl group may be bonded to this phenyl group.

<The synthesis method of the compound represented by general formula (1-1) and (1-2) (1)>

<Synthesis of 4- (4-bromophenyl) pyridine or 4- (3-bromophenyl) pyridine>

First, a zinc chloride complex of pyridine is synthesized in the following Reaction Scheme (1), and then a zinc chloride complex of pyridine and 1,4-dibromobenzene or 1,3-dibromobenzene are reacted in the following Reaction Scheme (2). By doing so, 4- (4-bromophenyl) pyridine or 4- (3-bromophenyl) pyridine can be synthesized. Further, "ZnCl _2? TMEDA" in the reaction formula (1) is the Tet-methyl-ethylenediamine complex of zinc chloride. Although the synthesis method using 4-bromopyridine as a raw material is illustrated here, 4- (4-bromophenyl) pyridine or 4- (3-bromophenyl) pyridine can also be synthesize | combined by using 4-iodopyridine as a raw material. Can be. In addition, although 1, 4- dibromo benzene or 1, 3- dibromo benzene was used as a raw material here, synthesis | combination also uses 1-bromo-4- iodine benzene or 1-bromo-3- iodine benzene. can do. Moreover, instead of making zinc chloride complex of pyridine react with 1, 4- dibromo benzene or 1, 3- dibromo benzene, the coupling reaction which makes 4-pyridine boronic acid and 4-pyridine boronic acid ester react is carried out. It can also be obtained by

[Chemical Formula 12]

In said reaction formula (1), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group.

<Synthesis of anthracene-9,10-diboronic acid (or boronic acid ester) in which 2-position is substituted with Ar>

First, as shown in following Reaction formula (3), 2- (naphthalen-2-yl) -9,10-dibromoanthracene is obtained by bromination of the anthracene substituted by 2-position using a suitable brominating agent. Suitable brominating agents include bromine or N-brominated succinimide (NBS). Here, although anthracene in which 2-position was substituted by 2-naphthyl group was illustrated, 9,10- dibromo anthracene in which various Ar was introduce | transduced by changing a raw material suitably can be obtained.

[Formula 13]

In addition, the anthracene which has a substituent at 2-position (2-naphthyl group in the said Reaction formula (3)) is boronic acid (or boronic acid ester) of the anthracene 2-position substituted by halogen or triflate and the group corresponding to the said substitution base. By the Suzuki coupling of), anthracene having a substituent at the 2-position can be synthesized. Moreover, as another method, the synthesis | combining method by Negishi coupling of the anthracene substituted by the halogen or triflate 2-position with the zinc complex of the group corresponding to the said substituent is mentioned. In addition, a synthesis method by Suzuki coupling of a group corresponding to the substituent substituted with 2-anthracene boronic acid (or boronic acid ester) with halogen or triflate, and furthermore, substituted with 2-anthracene zinc complex and halogen or triflate The synthesis method by Negishi coupling of group corresponding to the said substituent is also mentioned.

Next, as shown in following Reaction Formula (4), 2- (naphthalen-2-yl) -9,10-dibromoanthracene is lithiated using an organolithium reagent, or magnesium or an organic magnesium reagent is used. 2- (naphthalen-2-yl) anthracene-9,10-diboronic acid ester can be synthesized by reacting with Grignard reagent and reacting with trimethyl borate, triethyl borate or triisopropyl borate. Furthermore, 2- (naphthalen-2-yl) anthracene-9,10-diboronic acid is hydrolyzed by this 2- (naphthalen-2-yl) anthracene-9,10-diboronic acid ester in the following reaction formula (5). Can be synthesized.

[Formula 14]

In said reaction formula (4), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group.

In addition, as shown in the above reaction formula (6), 2- (naphthalen-2-yl) -9,10-dibromoanthracene is lithiated using an organolithium reagent, or magnesium or an organic magnesium reagent is used. To Grignard reagent, and reacted with bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane to yield another 2- (naphthalen-2-yl ) Anthracene-9,10- diboronic acid ester can be synthesize | combined. Moreover, as shown in following Reaction Formula (7), 2- (naphthalen-2-yl) -9,10-dibromoanthracene and bis (pinacolato) diboron or 4,4,5,5-tetramethyl The same 2- (naphthalen-2-yl) anthracene-9,10-diboronic acid ester can be synthesize | combined by carrying out a coupling reaction of -1,3,2-dioxaborolane using a palladium catalyst and a base.

[Formula 15]

In said reaction formula (6), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group.

Furthermore, in the above reaction formulas (4), (6) or (7), instead of bromide such as 2- (naphthalen-2-yl) -9,10-dibromoanthracene, chloride, iodide, or triple The acid can be synthesized in the same manner.

<Synthesis of Compounds According to the Present Invention by Suzuki Coupling Reaction>

Finally, as shown in the following reaction formula (8), 2- (naphthalen-2-yl) anthracene-9,10-diboronic acid or 2- (naphthalen-2-yl) anthracene synthesized as described above. In the present invention, 2-fold molar 4- (4-bromophenyl) pyridine or 4- (3-bromophenyl) pyridine is reacted with -9,10-diboronic acid ester in the presence of a palladium catalyst and a base. Related compounds can be synthesized.

[Formula 16]

Moreover, as shown in the said reaction formula (9), 2- (naphthalen-2-yl) -9,10-dibromoanthracene is a palladium catalyst to boronic acid or boronic acid ester of 2 times mole pyridylbenzene. By reacting with and in the presence of a base, the compound of the present invention can be synthesized. In addition, boronic acid or boronic acid ester of pyridyl benzene is 4- (4-bromophenyl) pyridine or 4- (3-bromophenyl) pyridine, and the said reaction formula (4)? It can synthesize | combine by the method according to (7).

[Formula 17]

Specific examples of the palladium catalyst used in the Suzuki coupling reaction include tetrakis (triphenylphosphine) palladium (O): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , palladium acetate (II): Pd (OAc) ₂ , tris (dibenzylideneacetone) 2 palladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) 2 palladium (O ) Chloroform complex: Pd ₂ (dba) _3- CHCl ₃ , or bis (dibenzylidene acetone) palladium (O): Pd (dba) ₂ is mentioned.

Moreover, in order to accelerate reaction, you may add a phosphine compound to these palladium compounds as needed. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (dit-butylphosphino) ferrocene, 1 -(N, N-dibutylaminomethyl) -2- (dit-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (dit-butylphosphino) ferrocene, 1,1'-bis (Dit-butylphosphino) ferrocene, 2,2'-bis (dit-butylphosphino) -1,1'-vinaphthyl, 2-methoxy-2 '-(dit-butylphosphino) -1,1'- vinapthyl or 2-dicyclohexyl phosphino-2 ', 6'- dimethoxy biphenyl is mentioned.

Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxy, sodium t-butoxide, sodium acetate, potassium triphosphate, or Potassium fluoride is mentioned.

In addition, specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butylmethyl ether And 1,4-dioxane, methanol, ethanol, cyclopentylmethyl ether or isopropyl alcohol. These solvents can be selected suitably, may be used independently, and may be used as a mixed solvent.

<The synthesis method of the compound represented by general formula (1-1) and (1-2) (2)>

<Synthesis of anthracene-9,10-diazine complex with 2 position substituted by Ar>

First, as shown in following Reaction Formula (10), 2- (naphthalen-2-yl) -9,10-dibromoanthracene is lithiated using an organolithium reagent, or magnesium or an organic magnesium reagent is used. 2- (naphthalen-2-yl) anthracene-9,10-diazine complex can be synthesized by reacting with Grignard reagent and zinc chloride or zinc chloride tetramethylethylenediamine complex (ZnCl ₂ ? TMEDA). .

[Formula 18]

In said reaction formula (10), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group. In addition, instead of bromide such as 2- (naphthalen-2-yl) -9,10-dibromoanthracene, chloride or iodide can be synthesized in the same manner. Moreover, about the method of introduce | transducing another substituent (Ar) in the 2 position of anthracene, it is the same as that described in the column of the said Suzuki coupling reaction.

<Synthesis of Compound According to the Invention by Negishi Coupling Reaction>

Finally, as shown in the following reaction formula (11), 2- (naphthalen-2-yl) anthracene-9,10-diazine complex synthesized as described above was 2-fold molar 4- (4 Compounds related to the present invention can be synthesized by reacting -bromophenyl) pyridine or 4- (3-bromophenyl) pyridine in the presence of a palladium catalyst.

[Formula 19]

Moreover, as shown in the said Reaction formula (12), 2- (naphthalen-2-yl) -9,10-dibromoanthracene is 4- (4-bromophenyl) pyridine or 4- (3-bromo The compound related to this invention can be synthesize | combined by making 2-molar 4-pyridylbenzenezinc complex synthesize | combined by phenyl) pyridine by the method according to the said Reaction formula (10) in presence of a palladium catalyst.

[Formula 20]

Specific examples of the palladium catalyst used in the Negishi coupling reaction include tetrakis (triphenylphosphine) palladium (O): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , palladium acetate (II): Pd (OAc) ₂ , tris (dibenzylideneacetone) 2 palladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) 2 palladium (O ) Chloroform complex Pd ₂ (dba) ₃ -CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (trit-butylphosphino) palladium (O), or (1,1 ) -Bis (diphenylphosphino) ferrocene) dichloropalladium (II) is mentioned.

In addition, specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butylmethyl ether And cyclobenzyl methyl ether or 1,4-dioxane. These solvents can be selected suitably, may be used independently, and may be used as a mixed solvent.

Moreover, although the thing of at least one part of hydrogen atom is substituted by deuterium is contained in the compound of this invention, such a compound can be synthesize | combined similarly to the above by using the deuterated raw material where desired.

3. Organic Field  Light emitting element

The anthracene compound which has a pyridylphenyl group which concerns on this invention can be used as a material of an organic electroluminescent element, for example. EMBODIMENT OF THE INVENTION Hereinafter, the organic electroluminescent element which concerns on this embodiment is demonstrated in detail based on drawing. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to the present embodiment.

<Structure of Organic Electroluminescent Element>

The organic electroluminescent element 100 shown in FIG. 1 includes a substrate 101, an anode 102 formed on the substrate 101, a hole injection layer 103 formed on the anode 102, and a hole injection layer. The hole transport layer 104 formed on the 103, the light emitting layer 105 formed on the hole transport layer 104, the electron transport layer 106 formed on the light emitting layer 105, and the electrons formed on the electron transport layer 106. The injection layer 107 and the cathode 108 formed on the electron injection layer 107 are provided.

In addition, the organic electroluminescent element 100 reverses the manufacturing order, for example, the board | substrate 101, the cathode 108 formed on the board | substrate 101, and the electron injection layer formed on the cathode 108, for example. 107, the electron transport layer 106 formed on the electron injection layer 107, the light emitting layer 105 formed on the electron transport layer 106, the hole transport layer 104 formed on the light emitting layer 105, and holes The structure which has the hole injection layer 103 formed on the transport layer 104, and the anode 102 formed on the hole injection layer 103 may be sufficient.

It is not necessary for each of the above layers to be present, 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. Layer 103 and hole transport layer 104 are optionally formed layers. In addition, each layer may be a single layer or may be a plurality of layers.

As an aspect of the layer which comprises an organic electroluminescent element, it is a board | substrate / anode / hole other than the structural aspect of the above-mentioned "substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode". Transport layer / light emitting layer / electron transport layer / electron injection layer / anode &quot;, &quot; substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode &quot;, &quot; 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 transport layer / cathode "," substrate / positive / Light emitting layer / an electron injection and may be configured of a layer / cathode "mode.

<Substrate in Organic Electroluminescent Element>

The substrate 101 serves as a support for the organic electroluminescent element 100, and typically quartz, glass, metal, plastic, or the like is used. The board | substrate 101 is formed in plate shape, film shape, or sheet shape according to the objective, and a glass plate, a metal plate, metal foil, a plastic film, a plastic sheet, etc. are used, for example. Especially, the plate made from transparent synthetic resins, such as a glass plate and polyester, a polymethacrylate, a polycarbonate, and a polysulfone, is preferable. Soda-lime glass, an alkali free glass, etc. are used as it is a glass substrate, and since thickness should just be sufficient to maintain mechanical strength, for example, what is necessary is just 0.2 mm or more. As an upper limit of thickness, it is 2 mm or less, for example, Preferably it is 1 mm or less. Since a non-alkali glass is preferable because side preferably less ion elution from glass pieces for the materials of glass, SiO _2, such as soda lime glass is also on the market was subjected to the barrier coat may be this. In order to increase the gas barrier property, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface thereof, and in particular, a plate, film or sheet made of synthetic resin having low gas barrier property may be provided. When using as a film, it is preferable to form a gas barrier film.

<Anode in Organic Electroluminescent Element>

The anode 102 serves to inject holes into the light emitting layer 105. In addition, when the hole injection layer 103 and / or the hole transport layer 104 are formed between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 via these.

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

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 about 300 Ω / □ functions as an element electrode, but since it is possible to supply a substrate of about 10 Ω / □, for example, 100? 5 Ω / □ preferably 50? It is particularly preferable to use a low resistance product of 5 Ω / □. The thickness of the ITO can be arbitrarily selected according to the resistance value, but is usually 100? It is often used between 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescent element>

The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or into the hole transport layer 104. The hole transport layer 104 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 via 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 or two or more of the hole injection and transport materials, or a mixture of the hole injection and transport materials and the polymer binder. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection and transport material to form a layer.

As the hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes given an electric field, so that the hole injection efficiency is high and the injected holes are preferably transported efficiently. For this purpose, it is preferable that the ionization potential is small, the hole mobility is large, and further, the stability is excellent, and impurities which become traps are hardly generated during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, a hole injection layer of a compound, a p-type semiconductor, and an organic electroluminescent element conventionally used as a charge transport material for holes in a photoconductive material And any known ones used in the hole transport layer. Specific examples of these include biscarbazole derivatives such as carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole), bis (N-arylcarbazole) or bis (N-alkylcarbazole), and triarylamine Derivatives (Polymer having 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di having an aromatic tertiary amino group in the main chain or side chain) (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'- Triphenylamine derivatives such as diphenyl-1,1'-diamine, 4,4 ', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine, stilbene derivatives and phthalocyanine derivatives such as star burst amine derivatives (Metal free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole induction Heterocyclic compounds such as sieves, porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonates and styrene derivatives having a monomer in the side chain, polyvinylcarbazole, polysilane and the like are preferable, but thin films required for the production of light emitting devices The compound is not particularly limited as long as it is a compound capable of forming a compound, injecting holes from the anode, and further transporting holes.

It is also known that the conductivity of the organic semiconductor is strongly influenced by its doping. Such an organic semiconductor matrix material is composed of a compound having good electron donating or a compound having good electron acceptability. For the doping of electron donor materials, strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) Known (see, eg, M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998) and J. Blochwitz). , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998). These produce so-called holes in accordance with the electron transfer process in the electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material changes very greatly. As the matrix material having hole transporting properties, for example, a benzidine derivative (TPD, etc.) or a star burst amine derivative (TDATA, etc.), or a specific metal phthalocyanine (particularly, zinc phthalocyanine ZnPc, etc.) is known (Japanese Patent Laid-Open Publication). 2005-167175).

<Light Emitting Layer in Organic Electroluminescent Element>

The light emitting layer 105 emits light by recombining the holes injected from the anode 102 and the electrons injected from the cathode 108 between the electrodes given an electric field. The material for forming the light emitting layer 105 may be a compound (light emitting compound) that is excited by light recombination of holes and electrons and emits light, and can form a stable thin film shape, and also has strong light emission in a solid state (fluorescence and / Or phosphorescent) efficiency.

The light emitting layer may be either a single layer or a plurality of layers, and is formed of a light emitting material (host material, dopant material), respectively. The host material and the dopant material may be either one kind or a plurality of combinations, respectively. The dopant material may be either contained entirely in the host material or partially contained. As a doping method, although it can form by co-deposition with a host material, you may vapor-deposit simultaneously after mixing with a host material previously.

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 It is 80-99.9 weight%, More preferably, it is 90-99.9 weight%.

The amount of dopant material used varies depending on the type of dopant material, and may be determined in accordance with the properties of the dopant material. The amount of dopant used is preferably 0.001? 50 weight%, More preferably, it is 0.05? 20 wt%, more preferably 0.1? 10 wt%. If it is the said range, it is preferable at the point which can prevent concentration quenching phenomenon, for example.

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

Although it does not specifically limit as a host material, Condensed ring derivatives, such as anthracene and a pyrene, which were previously known as a light emitter, Metal chelate oxynoid compound, such as tris (8-quinolinolato) aluminum, Bisstyryl anthracene derivative, Bisstyryl derivatives such as distyrylbenzene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, p In the rolopyrrole derivative, the fluorene derivative, the benzofluorene derivative, and the polymer system, a polyphenylene vinylene derivative, a polyparaphenylene derivative, and a polythiophene derivative are preferably used.

In addition, as a host material, it can select suitably from among the compounds described in the chemical industry June 2004 page 13, and the references listed here.

In addition, the dopant material is not particularly limited, and a known compound can be used, and can be selected from various materials according to the desired emission color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, benzothiazole Derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, Bisstyryl derivatives, such as a tetraphenyl butadiene derivative, a cyclopentadiene derivative, a bisstyryl anthracene derivative, and a distyryl benzene derivative (JP-A-1-245087), a bisstyryl arylene derivative (JP-A-5) 2-247278), diazaindane derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimethylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-triple) Isobenzofuran derivatives, such as fluoromethylphenyl) isobenzofuran and phenylisobenzofuran, dibenzofuran derivative, 7-dialkylaminocoumarin derivative, 7-piperidinocoumarin derivative, 7-hydroxycoumarin derivative, 7-meth Coumarin derivatives, such as methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolyl coumarin derivatives, 3-benzoimidazolyl coumarin derivatives, 3-benzooxazolyl coumarin derivatives, dicyano methylene pyran derivatives, and dicyano methylenethio Pyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyryllium derivatives, carbostyryl derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, Quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, propylidine derivatives, 1,2,5-thiadiazolopyrene derivatives, pyrromethene derivatives Sieves, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violatron derivatives, phenazine derivatives, acridon derivatives, deazaflavin derivatives, fluorene derivatives and benzofluorene derivatives.

For example, by color light, blue? Examples of the cyan dopant material include aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene, derivatives thereof, furan, pyrrole, thiophene, silol, and 9-sila Fluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazolepyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pi Aromatic heterocyclic compounds such as rolopyridine and thioxanthene, derivatives thereof, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles, thiadiazoles, carbazoles, Azole derivatives such as oxazole, oxadiazole and triazole and metal complexes thereof and N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1 ' Aromatic amine derivatives represented by diamines.

Again, rust? Naphthacene derivatives such as yellow dopant materials, coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridon derivatives, quinacridone derivatives and rubrene Can be mentioned, and further said the blue? The compound which introduce | transduced the substituent which enables long wavelengths, such as an aryl group, a heteroaryl group, an aryl vinyl group, an amino group, and a cyano group, to the compound illustrated as a cyan dopant material is also mentioned as a preferable example.

Furthermore, the back? Examples of the red dopant material include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acidimide, perinone derivatives, Eu complexes such as acetylacetone, benzoylacetone and phenanthroline as ligands. Rare earth complexes, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its flexible bodies, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, Diazaflavin derivatives, coumarin derivatives, quinacridone derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violatron derivatives, phenazine derivatives, phenoxazone derivatives and thia And diazolopyrene derivatives. Turquoise and rust? The compound which introduce | transduced the substituent which enables long wavelengths, such as an aryl group, heteroaryl group, an aryl vinyl group, an amino group, and a cyano group, is mentioned as a preferable example to the compound illustrated as a yellow dopant material. Furthermore, the phosphorescent metal complex which made iridium and platinum the center metal represented by tris (2-phenylpyridine) iridium (III) is also a preferable example.

In addition, as a dopant, it can select suitably from among the compounds described in the chemical industry June 2004 page 13, the references mentioned here, etc., and can use.

Among the above-described dopant materials, particularly preferred are perylene derivatives, borane derivatives, amine-containing styryl derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, iridium complexes and platinum complexes.

Examples of the perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene and 3,10-diphenyl Perylene, 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) etc. are mentioned.

Japanese Unexamined Patent Publication No. Hei 11-97178, Japanese Unexamined Patent Publication No. 2000-133457, Japanese Unexamined Patent Publication No. 2000-26324, Japanese Unexamined Patent Publication No. 2001-267079, Japanese Unexamined Patent Publication No. 2001-267078, Perylene derivatives described in Japanese Patent Application Laid-Open No. 2001-267076, Japanese Patent Laid-Open No. 2000-34234, Japanese Patent Laid-Open No. 2001-267075, Japanese Patent Laid-Open No. 2001-217077, or the like can also be used.

As the borane derivative, for example, 1,8-diphenyl-10- (dimethyl boryl) anthracene, 9-phenyl-10- (dimethyl boryl) anthracene, 4- (9'-anthryl) di Mesitylborylnaphthalene, 4- (10'-phenyl-9'-anthryl) dimethylborylnaphthalene, 9- (dimethoxylboryl) anthracene, 9- (4'-biphenylyl) -10- (di Mesityl boryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) -10- (dimethyl boryl) anthracene, etc. are mentioned.

Moreover, the borane derivative described in pamphlet of international publication 2000/40586 can also be used.

As the amine-containing styryl derivative, for example, 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 (9-ethyl-carbazolevinylene) -biphenyl, 4,4'-bis (9-phenyl-3-carbazolevinylene) -biphenyl etc. are mentioned.

Moreover, the amine containing styryl derivative described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc. can also be used.

Examples of the aromatic amine derivatives include N, N, N, N-tetraphenylanthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, 9,10-bis ( 4-di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di- p-tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2 -Naphthyl) anthracene, [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenyl Amine, [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- And diphenylaminonaphthalen-2-yl] -p-terphenyl.

Moreover, the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888 etc. can also be used.

Examples of coumarin derivatives include coumarin-6 and coumarin-334.

Moreover, the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, Unexamined-Japanese-Patent No. 6-298758, etc. can also be used.

As a pyran derivative, following DCM, DCJTB, etc. are mentioned.

[Formula 21]

Moreover, Unexamined-Japanese-Patent No. 2005-126399, Unexamined-Japanese-Patent No. 2005-097283, Unexamined-Japanese-Patent No. 2002-234892, Unexamined-Japanese-Patent No. 2001-220577, Unexamined-Japanese-Patent No. 2001-081090, and Unexamined-Japanese-Patent You may use the pyran derivative as described in patent publication 2001-052869 grade | etc.,.

Examples of the iridium complex include the following Ir (ppy) ₃ and the like.

[Formula 22]

Iridium described in Japanese Unexamined Patent Publication No. 2006-089398, Japanese Unexamined Patent Publication No. 2006-080419, Japanese Unexamined Patent Publication No. 2005-298483, Japanese Unexamined Patent Publication No. 2005-097263, Japanese Unexamined Patent Publication No. 2004-111379, and the like. Complexes may also be used.

The following PtOEP etc. are mentioned as a platinum complex.

(23)

Platinum disclosed in Japanese Unexamined Patent Publication No. 2006-190718, Japanese Unexamined Patent Publication No. 2006-128634, Japanese Unexamined Patent Publication No. 2006-093542, Japanese Unexamined Patent Publication No. 2004-335122, Japanese Unexamined Patent Publication No. 2004-331508, etc. Complexes may also be used.

<Electron injection layer and electron transport layer in organic electroluminescent element>

The electron injection layer 107 plays a role of efficiently injecting electrons traveling from the cathode 108 into the light emitting layer 105 or the electron transporting layer 106. The electron transport layer 106 serves to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 via 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 two or more kinds of electron transport and injection materials, or a mixture of the electron transport and injection materials and a polymer binder.

The electron injection and transport layer is a layer in which electrons are injected from the cathode and is responsible for transporting electrons. The electron injection efficiency is high, and it is preferable to transport the injected electrons efficiently. For this purpose, it is preferable that the material has a high electron affinity, a high electron mobility, further excellent stability, and hardly generates impurities which become traps during production and use. However, when considering the balance of transport of holes and electrons, the main role is to effectively prevent the holes from the anode flowing to the cathode side without recombination. The effect of improving is equivalent to that of a material having a high electron transport ability. Therefore, the electron injection-transport layer in this embodiment may also contain the function of the layer which can effectively block the movement of a hole.

As a material (electron transport material) which forms the electron carrying layer 106 or the electron injection layer 107, the compound represented by the said General formula (1) can be used. Content of the compound represented by the said General formula (1) in the electron carrying layer 106 or the electron injection layer 107 differs according to the kind of compound, and may be determined according to the characteristic of the compound. The reference for the content of the compound represented by the general formula (1) is preferably 1 to the entire electron transport layer material (or the electron injection layer material). 100 weight%, More preferably, it is 10? 100 wt%, more preferably 50? 100 wt%, particularly preferably 80? 100% by weight. When the compound represented by the said General formula (1) is not used individually (100 weight%), what is necessary is just to mix the other material described in detail below.

The material for forming another electron transport layer or electron injection layer may be arbitrarily selected from compounds conventionally used as electron transport compounds in light conductive materials, electron injection layers of organic electroluminescent devices, and known compounds used in electron transport layers. Can be used.

As a material used for an electron carrying layer or an electron injection layer, the compound which consists of an aromatic ring or a hetero aromatic ring which consists of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, a pyrrole derivative, and its condensed ring derivative And at least one selected from metal complexes having an electron-accepting nitrogen. Specifically, styryl system aromatic ring derivatives represented by condensed ring aromatic ring derivatives such as naphthalene and anthracene, 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives and naphthalimide Derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives. Examples of the metal complex having an electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. . These materials are used alone, but may be used in combination with different materials. Especially, anthracene derivatives, such as 9,10-bis (2-naphthyl) anthracene, and styryl type aromatic derivatives, such as 4,4'-bis (diphenylethenyl) biphenyl, 4,4'-bis (N Carbazole derivatives such as -carbazolyl) biphenyl and 1,3,5-tris (N-carbazolyl) benzene are preferably used in view of durability.

Moreover, as a specific example of another electron transfer compound, a pyridine derivative, a naphthalene derivative, an anthracene derivative, a phenanthroline derivative, a perinone derivative, a coumarin derivative, a naphthalimide derivative, an anthraquinone derivative, a diphenoquinone derivative, a diphenylquinone Derivatives, perylene derivatives, oxadiazole 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 auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles Compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis (benzo [h] quinolin-2-yl) -9,9'- Spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives ( Oligopyridine derivatives such as tris (N-phenylbenzoimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine, bipyridine derivatives, terpyridine derivatives (1,3- Bis (4 '-(2,2': 6'2 "-terpyridinyl)) benzene, etc.), naphthyridine derivative (bis (1-naphthyl) -4- (1,8-naphthyridine-2) -Yl) phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, inoxide derivatives, bisstyryl derivatives, and the like.

Moreover, the metal complex which has an electron accepting nitrogen can also be used, For example, hydroxyazole complexes, such as a quinolinol type metal complex and a hydroxyphenyl oxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex And benzoquinoline metal complexes.

Although the material mentioned above is used independently, you may mix and use with a different material.

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

Quinolinol-based metal complexes are compounds represented by the following general formula (E-1).

[Formula 24]

In the formula, R ¹ ? R ⁶ is hydrogen or a substituent, M is Li, Al, Ga, Be or Zn, and n is 1? Is an integer of 3.

Specific examples of the quinolinol-based metal complexes include 8-quinolinolithium, 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-methylphenolate) aluminum , Bis (2-methyl-8-quinolinolato) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl -8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8-quinolinola Earth) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) alu 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-quinolinolato) (3,5-di-t-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenol Aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5, 6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholate) aluminum , Bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2,4-di Methyl-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-u-oxo-bis (2-methyl-8 -Quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-u-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2-methyl- 4-ethyl-8-quinolinolato) aluminum-u-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-qui Nolinorato) aluminum-u-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum- u-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-u-oxo- Bis (2-methyl-5-trifluoromethyl-8-quinol Linolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium, and the like.

The bipyridine derivative is a compound represented by the following general formula (E-2).

[Formula 25]

In the formula, G represents a simple bond or n-valued linking group, and n represents 2? Is an integer of 8. Moreover, the carbon atom which is not used for the bonding of pyridine-pyridine or pyridine-G may be substituted.

As G of general formula (E-2), the thing of the following structural formula is mentioned, for example. In addition, R in the following structural formula is respectively independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

[Formula 26]

Specific examples of the pyridine derivatives include 2,5-bis (2,2'-pyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilol and 2,5-bis (2,2 ' -Pyridin-6-yl) -1,1-dimethyl-3,4-dimethoxylsilol, 2,5-bis (2,2'-pyridin-5-yl) -1,1-dimethyl-3,4 -Diphenylsilol, 2,5-bis (2,2'-pyridin-5-yl) -1,1-dimethyl-3,4-dimethylsilol, 9,10-di (2,2'-pyridine -6-yl) anthracene, 9,10-di (2,2'-pyridin-5-yl) anthracene, 9,10-di (2,3'-pyridin-6-yl) anthracene, 9,10-di (2,3'-pyridin-5-yl) anthracene, 9,10-di (2,3'-pyridin-6-yl) -2-phenylanthracene, 9,10-di (2,3'-pyridine- 5-yl) -2-phenylanthracene, 9,10-di (2,2'-pyridin-6-yl) -2-phenylanthracene, 9,10-di (2,2'-pyridin-5-yl) 2-phenylanthracene, 9,10-di (2,4'-pyridin-6-yl) -2-phenylanthracene, 9,10-di (2,4'-pyridin-5-yl) -2-phenyl Anthracene, 9,10-di (3,4'-pyridin-6-yl) -2-phenylanthracene, 9,10-di (3,4'-pyridin-5-yl) -2-phenylanthracene, 3, 4-diphenyl-2,5-di (2,2'-pyridin-6-yl) thiophene, 3,4-diphenyl-2,5-di (2,3'- Naphthyridin-5-yl) thiophene, 6 ', 6' - di (2-pyridyl) 2,2 ': 4', 4 ": 2", 2 " '-, and the like quarter pyridine.

The phenanthroline derivative is a compound represented by the following general formula (E-3-1) or (E-3-2).

[Formula 27]

In the formula, R ¹ ? R ⁸ is hydrogen or a substituent, and adjacent groups may combine with each other to form a condensed ring, G represents a simple bond number or a linking group having n value, and n represents 2? Is an integer of 8. Moreover, as G of general formula (E-3-2), the same thing as what was demonstrated in the column of a bipyridine derivative is mentioned, for example.

Specific examples of the phenanthroline derivatives 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-phenanthrole Lin-5-yl) benzene, 9,9'-difluoro-bis (1,10-phenanthroline-5-yl), bartocouproin or 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 carrying layer and an electron injection layer is demonstrated. A material that obtains stable luminescence over a long period of time, and has excellent thermal stability and thin film formability is desired. Among the phenanthroline derivatives, the substituent itself has a two-dimensional structure, or a solid with a phenanthroline skeleton or with an adjacent substituent. It is preferable to have a three-dimensional solid structure by repulsion or to connect several phenanthroline skeleton. Moreover, when connecting several phenanthroline frame | skeleton, the compound containing the conjugated bond, substituted or unsubstituted aromatic hydrocarbon, and substituted or unsubstituted aromatic heterocyclic ring in a connection unit is more preferable.

Borane derivatives are compounds represented by the following general formula (E-4), and are disclosed in Japanese Unexamined Patent Publication No. 2007-27587.

[Formula 28]

In the formula, each of R ¹¹ and R ¹² is independently at least one of a hydrogen atom, an alkyl group, an aryl group which may be substituted, a substituted silyl group, a nitrogen-containing heterocyclic group which may be substituted, or a cyano group, and R ¹³ ? R ¹⁶ is each independently an alkyl group which may be substituted or an aryl group which may be substituted, X is an arylene group which may be substituted, and Y is an aryl group having 16 or less carbon atoms which may be substituted, substituted boryl group, or substituted Carbazole group may be present, and n is each independently 0? Is an integer of 3.

Among the compounds represented by the general formula (E-4), compounds represented by the following general formula (E-4-1), and the following general formula (E-4-1-1)? The compound represented by (E-4-1-4) is preferable. As a specific example, 9- [4- (4-dimethyl boryl naphthalen-1-yl) phenyl] carbazole, 9- [4- (4-dimethyl boryl naphthalen-1-yl) naphthalene-1- General] carbazole and the like.

[Formula 29]

In the formula, each of R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group, an aryl group which may be substituted, a substituted silyl group, a nitrogen-containing heterocyclic group which may be substituted, or a cyano group, and R ¹³ ? R ¹⁶ is each independently an alkyl group which may be substituted or an aryl group which may be substituted, and R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group, an aryl group which may be substituted, a substituted silyl group or may be substituted. At least one of a nitrogen-containing heterocyclic group or a cyano group, X ¹ is an arylene group having 20 or less carbon atoms which may be substituted, and n is each independently 0? Is an integer of 3, and M is each independently 0? Is an integer of 4.

[Formula 30]

In each formula, R ³¹ ? R ³⁴ is each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl.

Among the compounds represented by the following General Formula (E-4), compounds represented by the following General Formula (E-4-2) and compounds represented by the following General Formula (E-4-2-1) are preferable.

[Formula 31]

In formula, R <^11> and R <^12> are respectively independently a hydrogen atom, an alkyl group, the aryl group which may be substituted, the substituted silyl group, the nitrogen-containing heterocyclic group which may be substituted, or the cyano group, and are R <^13>- ? R <^16> is respectively independently the alkyl group which may be substituted, or the aryl group may be substituted, X <^1> is the C20 or less arylene group which may be substituted, and n is respectively independently 0? Is an integer of 3.

[Formula 32]

In the formula, R ³¹ ? R ³⁴ is each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl.

Also in the compound represented by the said General formula (E-4), the compound represented by the following general formula (E-4-3), Furthermore, the said general formula (E-4-3-1) or (E-4-3-2) The compound represented by is preferable.

[Formula 33]

In the formula, each of R ¹¹ and R ¹² is independently at least one of a hydrogen atom, an alkyl group, an aryl group which may be substituted, a substituted silyl group, a nitrogen-containing heterocyclic group which may be substituted, or a cyano group, and R ¹³ ? R ¹⁶ is each independently an alkyl group which may be substituted or an aryl group which may be substituted, X ¹ is an arylene group having 10 or less carbon atoms which may be substituted, and Y ¹ is an aryl group having 14 or less carbon atoms which may be substituted And n are each independently 0? Is an integer of 3.

[Formula 34]

In each formula, R ³¹ ? R ³⁴ is each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl.

A benzimidazole derivative is a compound represented by the following general formula (E-5).

[Formula 35]

In the formula, Ar ¹ ? Ar ³ is independently hydrogen or C 6? 30 is aryl. In particular, the benzimidazole derivative which is anthryl which Ar <^1> may substitute is preferable.

6 carbon atoms? Specific examples of the aryl of 30 are phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5- Il, Fluoren-1-yl, Fluoren-2-yl, Fluoren-3-yl, Fluoren-4-yl, Fluoren-9-yl, Penalen-1-yl, Penalen-2-yl , 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthene-1-yl, fluorine Lanten-2-yl, Fluoranthen-3-yl, Fluoranthen-7-yl, Fluoranthen-8-yl, Triphenylen-1-yl, Triphenylen-2-yl, Pyrene-1 -Day, pyren-2-yl, pyren-4-yl, chryssen-1-yl, chrysen-2-yl, chrysene-3-yl, chryssen-4-yl, chrysene-5-yl, Chrysen-6-yl, naphthace-1-yl, naphthace-2-yl, naphthacene-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, penta Sen-1-yl, pentacene-2-yl, pentacene-5-yl, pentacene-6-yl.

Specific examples of the benzimidazole derivatives include 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalene) -2-yl) anthracene-9-yl) phenyl) -1-phenyl-lH-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -1-phenyl-lH-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracene-9-yl) -1,2-diphenyl-lH-benzo [d] imidazole, 1 -(4- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -2-phenyl-lH-benzo [d] imidazole, 2- (4- (9,10-di (naphthalene- 2-yl) anthracen-2-yl) phenyl) -1-phenyl-lH-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) Phenyl) -2-phenyl-1H-benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [d ] Imidazole.

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 the reducing substance, various kinds can be used as long as they have a constant reducing property. Examples of the reducing substance include alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, and alkaline earth metals. At least one selected from the group consisting of halides, 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 can be preferably used.

Preferred reducing materials include alkali metals such as Na (work function 2.36 eV), K (copper 2.28 eV), Rb (copper 2.16 eV) or Cs (copper 1.95 eV), and Ca (copper 2.9 eV), Sr (copper Alkaline earth metals, such as 2.0-2.5 eV) or Ba (copper 2.52 eV), and it is especially preferable that a work function is 2.9 eV or less. Among these, the more preferable reducing substance is K, Rb or Cs alkali metal, More preferably, it is Rb or Cs, Most preferably, it is Cs. In particular, these alkali metals have a high reducing ability, and a relatively small amount of the alkali metal is added to a material forming the electron transporting layer or the electron injection layer, thereby improving the emission luminance and extending the life of the organic EL device. In addition, as a reducing material having a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, and in particular, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs and Combinations of Na and K are preferred. By including Cs, reduction ability can be exhibited efficiently, and addition to the material which forms an electron carrying layer or an electron injection layer improves the luminescence brightness and long lifetime in an organic EL element.

<Cathode in organic electroluminescent element>

The cathode 108 plays a role of injecting electrons into the light emitting layer 105 via 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 is a substance capable of injecting electrons into the organic layer efficiently. The same material as the material 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 alloys) , Aluminum-lithium alloys such as magnesium-indium alloy and lithium fluoride / aluminum). Lithium, sodium, potassium, cesium, calcium, magnesium or alloys containing these low work function metals are effective to increase the electron injection efficiency to improve device characteristics. However, these low work function metals are often unstable in the atmosphere. In order to improve this point, for example, a method of doping a small amount of lithium, cesium or magnesium in the organic layer to use an electrode having high stability is known. 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.

In addition, for electrode protection, metals such as platinum, gold, silver, steel, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol and vinyl chloride And laminating a hydrocarbon-based high molecular compound and the like can be given as preferable examples. The production method of these electrodes is not particularly limited as long as it can conduct, such as resistance heating, electron beam beam, sputtering, ion plating, and coating.

<Binder to be used in each layer>

The above materials used in the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer may form each layer alone, but as the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcar Basezol), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS Dispersed solvent-soluble resins such as resins and polyurethane resins, curable resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins and silicone resins It is possible.

<Method of manufacturing organic electroluminescent element>

Each layer constituting the organic electroluminescent element is formed by a method such as deposition, resistive heating, electron beam deposition, sputtering, molecular lamination, printing, spin coating or casting, coating, or the like. It can be formed by forming a thin film. The film thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material. It is the range of 5000 nm. The film thickness can usually be measured by a crystal oscillation film thickness measuring device or the like. When thinning using the vapor deposition method, the vapor deposition conditions differ depending on the kind of material, the crystal structure and the associative structure to which the film is intended. Deposition conditions are generally +50? + 40 ° C., vacuum degree 10 ⁻⁶ ? 10 ^-3 Pa, Deposition Rate 0.O1? 50 nm / second, substrate temperature -150? + 300 ° C., film thickness of 2 nm? It is preferable to set suitably in the range of 5 micrometers.

Next, as an example of a method for producing an organic electroluminescent device, a method of manufacturing an organic electroluminescent device comprising a light emitting layer / electron transporting layer / electron injection layer / cathode composed of an anode / hole injection layer / hole transport layer / host material and a dopant material Explain. On a suitable substrate, a thin film of a positive electrode material is formed by vapor deposition or the like to produce a positive electrode, and then a thin film of a hole injection layer and a hole transport layer is formed on the positive electrode. The host material and the dopant material are co-deposited thereon to form a thin film to form a light emitting layer. An electron transporting layer and an electron injecting layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like to form a cathode. A target organic electroluminescent element is obtained. In addition, at the time of preparation of the organic electroluminescent element mentioned above, it can also manufacture in order of a cathode, an electron injection layer, an electron carrying layer, a light emitting layer, a hole transporting layer, a hole injection layer, and an anode in reverse order.

In the case where a direct current voltage is applied to the organic electroluminescent element thus obtained, the anode may be applied with the polarity of + and the cathode of-, and the voltage 2? When about 40 V is applied, light emission can be observed on the transparent or translucent electrode side (anode or cathode, and both). This organic electroluminescent element emits light even when a pulse current or an alternating current is applied. In addition, the waveform of the alternating current to apply may be arbitrary.

<Application example of organic electroluminescent element>

Moreover, this invention is applicable also to the display apparatus provided with organic electroluminescent element, the lighting apparatus provided with organic electroluminescent element, etc.

The display device or the lighting device provided with the organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element and the known drive device according to the present embodiment, and can be manufactured by direct current drive, pulse drive, and alternating current drive. The known driving method can be used as appropriate.

As a display apparatus, flexible displays, such as a panel display, such as a color flat panel display, and a flexible color organic electroluminescent (EL) display, etc. are mentioned (for example, Unexamined-Japanese-Patent No. 10-335066). , Japanese Unexamined Patent Publication No. 2003-321546, Japanese Unexamined Patent Publication No. 2004-28l086, etc.). Moreover, as a display system of a display, a matrix and / or a segment system etc. are mentioned, for example. In addition, the matrix display and the segment display may coexist in the same panel.

The matrix means that pixels for display are arranged two-dimensionally, such as a lattice shape or a mosaic shape, and displays a character and an image by a set of pixels. The shape and size of the pixel is determined depending on the application. For example, for pixels and images of personal computers, monitors, and televisions, rectangular pixels with one side of 300 μm or less are usually used, and for large displays such as display panels, pixels with one side of mm order can be used. do. In the case of monochrome display, pixels of the same color may be arranged. In the case of color display, pixels of red, green, and blue are arranged and displayed. In this case, there are typically delta types and stripe types. The matrix driving method may be either a linear sequential driving method or an active matrix. The linear sequential drive has an advantage of a simple structure. However, when the operation characteristics are taken into consideration, the active matrix may be excellent. Therefore, it is necessary to use it separately according to the use.

In the segment system (type), a pattern is formed to display predetermined information, and the determined area is made to emit light. For example, the time and temperature display in a digital clock or a thermometer, operation state display of an audio device, an electronic cooker, etc., a panel display of an automobile, etc. are mentioned.

Examples of the lighting device include lighting devices such as indoor lighting, backlights of liquid crystal displays, etc. See Published Patent Publication No. 2004-119211 et al.). The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light by itself, and is used for a liquid crystal display, a clock, an audio device, an automobile panel, a display panel, a cover, and the like. In particular, as a backlight for a liquid crystal display device, and a personal computer use in which a thinning is a problem, the backlight using the light emitting element according to the present embodiment is considered in view of the fact that the thinning is difficult because the conventional type is a fluorescent lamp or a light guide plate. It is characterized by being thin and lightweight.

[Example]

First, the synthesis example of the pyridylphenyl substituted anthracene compound used in the Example is demonstrated below.

<Synthesis example of the compound represented by Formula (1-1-10)>

[Formula 36]

<Synthesis of 4- (4-bromophenyl) pyridine>

To a flask containing 4-iodinepyridine (7.0 g) and THF (32 mL), 2 M isopropylmagnesium chloride THF solution (18.8 mL) was added dropwise while cooling and stirring in an ice bath under a nitrogen atmosphere. After completion of the dropwise addition, zinc chloride tetramethylethylenediamine complex (9.1 g) is added while cooling and stirring with ice water. Thereafter, the mixture was stirred at room temperature for 0.5 hour, 1,4-dibromobenzene (12.1 g) and Pd (PPh ₃ ) ₄ (0.2 g) were added, and the mixture was stirred at reflux for 2 hours. In order to cool the reaction solution to room temperature and remove the flask containing the catalyst, a solution in which approximately 2 times the molar amount of ethylenediamine tetraacetic acid-4 sodium salt dihydrate was dissolved in an appropriate amount of water (hereinafter, It is abbreviated as EDTA-4 Na aqueous solution). Furthermore, ethyl acetate was added and liquid separation operation was performed. The organic layer was concentrated with an evaporator, purified by silica gel column chromatography (toluene / ethyl acetate = 80/20 (volume ratio)), and then washed with heptane to give 4- (4-bromophenyl) pyridine (5.6 g) Got.

<2,2 '-(2-([1,1': 3 ', 1' '-terphenyl] -5'-yl) anthracene-9,10-diyl) bis (4,4,5,5- Synthesis of Tetramethyl-1,3,2-dioxaborolane)>

This boronic acid ester is the scheme 1-1 of Unexamined-Japanese-Patent No. 2009-275013? Synthesis was carried out according to scheme 1-5 (see pages 7 to 10 of the publication, paragraphs [0014] to [0017]).

<Synthesis of Compound Represented by Formula (1-1-10)>

2,2 '-(2-([1,1': 3 ', 1''-terphenyl]-5'-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetra Methyl-1,3,2-dioxaborolane) (67.0 g), 4- (4-bromophenyl) pyridine (57.4 g), Pd (PPh ₃ ) ₄ (5.9 g), potassium phosphate tribasic (86.6 g ), 1,2,4-trimethylbenzene (350 ml), t-butyl alcohol (70 ml) and water (14 ml) were placed in a flask, and the mixture was stirred at reflux for 2 hours under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature and filtered by addition of water and heptane. The obtained solid was washed with water and methanol, and then washed with toluene and chlorobenzene again. Furthermore, the compound "4,4 '-((2- [1,1': 3 ', 1" -terphenyl] -5'-yl) anthracene represented by (1-1-10) by recrystallization with chlorobenzene. -9,10-diyl) bis (4,1-phenylene) dipyridine "(22.1 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis example of the compound represented by Formula (1-1-7)>

[Formula 37]

<Synthesis of 2- (naphthalen-2-yl) anthracene>

2-bromoanthracene (31.1 g), 2-naphthaleneboronic acid, bis (dibenzylideneacetone) palladium (0) (0.35 g), tricyclohexylphosphine (0.34 g), phosphoric acid potassium (77.1 g), 1,2,4-trimethylbenzene (311 mL), t-butyl alcohol (62 mL), and water (12 mL) were put into the flask, and the mixture was stirred for 1 hour and a half at a reflux temperature under a nitrogen atmosphere. After the end of heating, the reaction solution was cooled to room temperature, water and heptane were added and filtered. The obtained solid was washed with water and heptane again, and then further washed with methanol to obtain 2- (naphthalen-2-yl) anthracene (36.7 g).

<Synthesis of 9,10-dibromo-2- (naphthalen-2-yl) anthracene>

Bromine (40.0 g) was added dropwise to a flask containing 2- (naphthalen-2-yl) anthracene (36.7 g) and chloroform (600 mL). After completion of the dropwise addition, the mixture was stirred for 9 and a half hours at room temperature, and water, sodium hydrogen sulfite and sodium hydrogen carbonate were added to terminate the reaction. Chloroform was distilled off under reduced pressure in the reaction solution, and the resulting solid was washed with water, washed with heptane, then with methanol, and further with toluene. Thereafter, recrystallization from xylene gave 9,10-dibromo-2- (naphthalen-2-yl) anthracene (32.1 g).

Synthesis of <2,2 '-(2- (naphthalen-2-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) >

9,10-dibromo-2- (naphthalen-2-yl) anthracene (32.1 g), bispinacolatodiborone (44.2 g), bis (dibenzylideneacetone) palladium (0) (2.0 g), tree A flask containing cyclohexylphosphine (2.0 g), potassium acetate (27.3 g), potassium carbonate (19.2 g) and anisole (420 mL) was heated and stirred at 130 ° C. for 3 hours under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature and suction filtered using a Kiriyama funnel covered with celite. The crystals obtained by adding heptane to the filtrate were separated by filtration, and 2,2 '-(2- (naphthalen-2-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl- 1,3,2-dioxaborolane) (31.5 g) was obtained.

<Synthesis of Compound Represented by Formula (1-1-7)>

2,2 '-(2- (naphthalen-2-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane (36.5 g) , 4- (4-bromophenyl) pyridine (36.9 g), Pd (PPh ₃ ) ₄ (3.8 g), potassium triphosphate (55.7 g), 1,2,4-trimethylbenzene (185 mL), t- Butyl alcohol (37 mL) and water (7.4 mL) were placed in a flask and stirred for 1 hour at reflux under a nitrogen atmosphere, after completion of heating, the reaction solution was cooled to room temperature and filtered by addition of water and heptane. The obtained solid was washed with water and methanol, and then recrystallized with nitrobenzene to give the compound "4,4 '-((2-naphthalen-2-yl) anthracene-9,10-diyl) represented by (1-1-7). Bis (4,1-phenylene) dipyridine "(25.0 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis example of the compound represented by Formula (1-1-2)>

[Formula 38]

<Synthesis of 2-([1,1'-biphenyl] -3-yl) anthracene>

2-bromoanthracene (31.1 g), 3-biphenylboronic acid (18.5 g), bis (dibenzylideneacetone) palladium (0) (0.22 g), tricyclohexylphosphine (0.22 g), tripotassium phosphate (49.5 g), 1,2,4-trimethylbenzene (200 mL), t-butyl alcohol (40 mL), and water (8 mL) were put into the flask, and the mixture was stirred for 1 hour and a half at a reflux temperature under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature, and filtered by suction with a Kiriyama funnel covered with celite. The obtained filtrate was distilled off under reduced pressure, and then washed with heptane to obtain 2-([1,1'-biphenyl] -3-yl) anthracene (32.0 g).

<Synthesis of 2-([1,1'-biphenyl] -3-yl) -9,10-dibromoanthracene>

Bromine (25.0 g) was added dropwise into a flask containing 2-([1,1'-biphenyl] -3-yl) anthracene (32.0 g) and chloroform (300 mL). After completion of the dropwise addition, the mixture was stirred overnight at room temperature, and water, sodium hydrogen sulfite and sodium hydrogen carbonate were added to terminate the reaction. Chloroform was distilled off under reduced pressure from the reaction solution, and the resulting solid was washed with water, washed with heptane, and then with methanol to remove 2-([1,1'-biphenyl] -3-yl) -9,10-di Bromoanthracene (34.0 g) was obtained.

<2,2 '-(2-([1,1'-biphenyl] -3-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2 Synthesis of Dioxaborolane)

2-([1,1'-biphenyl] -3-yl) -9,10-dibromoanthracene (34.0 g), bispinacolatodiborone (44.2 g), bis (dibenzylideneacetone) palladium ( 0) A flask containing (2.0 g), tricyclohexylphosphine (2.0 g), potassium acetate (27.4 g), potassium carbonate (19.2 g) and anisole (360 mL) was put under nitrogen atmosphere at 130 ° C. for 2 hours. It stirred by heating. After the completion of the heating, the reaction solution was cooled to room temperature and suction filtered using a Kiriyama funnel covered with celite. The crystals obtained by adding heptane to the filtrate were separated by filtration to obtain 2,2 '-(2- [1,1'-biphenyl] -3-yl) anthracene-9,10-diyl) bis (4,4, 5,5-tetramethyl-1,3,2-dioxaborolane) (31.0 g) was obtained.

<Synthesis of Compound Represented by Formula (1-1-2)>

2,2 '-(2- [1,1'-biphenyl] -3-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-di Oxaborolan) (24.3 g), 4- (4-bromophenyl) pyridine (23.4 g), Pd (PPh ₃ ) ₄ (2.4 g), tripotassium phosphate (35.4 g), 1,2,4-trimethyl Benzene (120 mL), t-butyl alcohol (24 mL) and water (5 mL) were put into the flask, and the mixture was stirred at reflux temperature under nitrogen atmosphere for 1 hour. After the completion of heating, the reaction solution was cooled to room temperature and filtered by addition of water and heptane. The obtained solid was washed with water and methanol, and then recrystallized with nitrobenzene to give the compound "4,4 '-((2- [1,1'-biphenyl] -3-yl) represented by (1-1-2)". Anthracene-9,10-diyl) bis (4,1-phenylene) dipyridine "(12.5 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis of Compound Represented by Formula (1-1-3)>

[Formula 39]

2,2 '-(2-([1,1'-biphenyl] -4-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2- Dioxaborolane) (58.2 g), 4- (4-bromophenyl) pyridine (56.2 g), Pd (PPh ₃ ) ₄ (2.31 g), tripotassium phosphate (106.0 g), 1,2,4- Trimethylbenzene (320 mL), t-butyl alcohol (65 mL) and water (65 mL) were put into the flask, and the mixture was stirred at reflux temperature under nitrogen atmosphere for 2 hours. After the completion of heating, the reaction solution was cooled to room temperature, water was added, suction filtration was performed, and a solid was collected. The obtained solid was washed with methanol and heated orthodichlorobenzene. Furthermore, the compound "4,4 '-((2-([1,1'-biphenyl] -4-yl) anthracene-9,10 represented by Formula (1-1-3) and recrystallized with orthodichlorobenzene was recrystallized. -Diyl) bis (4,1-phenylene)) dipyridine "(48.0 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis of Compound Represented by Formula (1-1-4)>

[Formula 40]

2,2 '-(2- (naphthalen-1-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (54.8 g ), 4- (4-bromophenyl) pyridine (55.3 g), Pd (PPh ₃ ) ₄ (5.69 g), potassium triphosphate (83.6 g), 1,2,4-trimethylbenzene (300 mL), t -Butyl alcohol (60 mL) and water (12 mL) were put into the flask, and the mixture was stirred for 1 hour at reflux under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature, and water was added to collect a precipitate by suction filtration. The obtained solid was washed with methanol, followed by ethyl acetate. Furthermore, after wash | cleaning with heated orthodichlorobenzene, it refine | purifies by activated carbon column chromatography (chlorobenzene), and the compound "4,4 '-((2-naphthalene-1-) represented by Formula (1-1-4). Yl) anthracene-9,10-diyl) bis (4,1-phenylene) dipyridine "(8.19 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis example of the compound represented by Formula (1-2-10)>

[Formula 41]

<Synthesis of 4- (3-bromophenyl) pyridine>

To a flask containing 4-iodinepyridine (6.0 g) and THF (30 mL), 2 M isopropyl magnesium chloride THF solution (16.1 mL) was added dropwise while cooling and stirring in an ice bath under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was stirred at room temperature for 0.5 hour. The flask was cooled again with ice water and with stirring, zinc chloride tetramethylethylenediamine complex (8.1 g) was added. Thereafter, the mixture was stirred at room temperature for 1 hour, 1-bromo-3-iodinebenzene (8.2 g) and Pd (PPh ₃ ) ₄ (1.O g) were added, and the mixture was stirred at reflux temperature for 2 hours. In order to cool the reaction solution to room temperature and remove the metal ions of the catalyst, a solution in which approximately 2 times the molar amount of ethylenediamine tetraacetic acid-4 sodium salt dihydrate was dissolved in an appropriate amount of water (after And abbreviated as EDTA-4Na aqueous solution) were added. Furthermore, ethyl acetate was added and liquid-separation was performed. The organic layer was concentrated with an evaporator and purified by silica gel column chromatography (toluene / ethyl acetate = 80/20 (volume ratio)) to give 4- (3-bromophenyl) pyridine (6.2 g).

<2,2 '-(2-([1,1': 3 ', 1 "-terphenyl] -5'-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetra Synthesis of Methyl-1,3,2-dioxaborolane)

This boronic acid ester is the scheme 1-1 of Unexamined-Japanese-Patent No. 2009-275013? Synthesis was carried out according to scheme 1-5 (see pages 7-10 of the publication, paragraphs [0014]-[0017]).

<Synthesis of Compound Represented by Formula (1-2-10)>

2,2 '-(2-([1,1': 3 ', 1 "-terphenyl] -5'-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl -1,3,2-dioxaborolane) (35.0 g), 4- (3-bromophenyl) pyridine (29.9 g), Pd (PPh ₃ ) ₄ (6.2 g), tripotassium phosphate (45.2 g) , 1,2,4-trimethylbenzene (175 mL), t-butyl alcohol (35 mL) and water (7 mL) were added to the flask and stirred for 1 hour at reflux under a nitrogen atmosphere. The liquid was cooled to room temperature, and water and toluene were added to carry out liquid separation, and the solvent was distilled off under reduced pressure in the organic layer, and purified by silica gel column chromatography (toluene / ethyl acetate = 80/20 (volume ratio)), 1-2-10) represented by the compound "4,4 '-((2- [1,1': 3 ', 1" -terphenyl] -5'-yl) anthracene-9,10-diyl) bis ( 3,1-phenylene) dipyridine "(14.2 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis example of the compound represented by Formula (1-2-7)>

[Formula 42]

<Synthesis of 2- (naphthalen-1-yl) anthracene>

2-bromoanthracene (10.0 g), 1-naphthaleneboronic acid (12.5 g), Pd (PPh ₃ ) ₄ (1.1 g), sodium carbonate (10.3 g), toluene (100 mL), ethanol (20 mL) and water (20 mL) was placed in a flask and stirred at reflux for 6 hours under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature and subjected to liquid separation. The organic layer was concentrated under reduced pressure and purified by silica gel chromatography (toluene). The eluate was concentrated under reduced pressure, and the solid obtained was recrystallized with tetrahydrofuran to obtain 2- (naphthalen-1-yl) anthracene (11.6 g).

<Synthesis of 9,10-dibromo-2- (naphthalen-1-yl) anthracene>

The flask containing 2- (naphthalen-2-yl) anthracene (7.0 g), iodine (30 mg) and tetrahydrofuran (120 mL) was cooled in an ice bath and N-bromosuccinimide (9.8 g) was added. It was. After stirring for 1 hour while cooling in an ice bath, the mixture was stirred at room temperature for 3 hours. The solid in the reaction solution was collected by suction filtration and washed with an aqueous sodium thiosulfate solution. This solid was dissolved in chlorobenzene and liquid separation was performed by adding saturated brine. The organic layer was concentrated under reduced pressure, and the precipitated solid was collected by suction filtration to obtain 9,10-dibromo-2- (naphthalen-1-yl) anthracene (4.4 g).

Synthesis of <2,2 '-(2- (naphthalen-1-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) >

9,10-dibromo-2- (naphthalen-1-yl) anthracene (3.2 g), bispinacolatodiborone (4.4 g), bis (dibenzylideneacetone) palladium (0) (0.2 g), tree A flask containing cyclohexylphosphine (0.2 g), potassium acetate (2.7 g), potassium carbonate (1.9 g) and anisole (15 mL) was heated and stirred at 130 ° C. for 7 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature and suction filtered using a Kiriyama funnel covered with celite. Heptane was added to the filtrate, and the obtained crystals were collected by suction filtration to obtain 2,2 '-(2- (naphthalen-1-yl) anthracene-9,10-diyl) bis (4,4,5,5 -Tetramethyl-1,3,2-dioxaborolane) (3.0 g) was obtained.

<Synthesis of Compound Represented by Formula (1-2-7)>

2,2 '-(2- (naphthalen-1-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaboron (3.0 g), 4- (3-bromophenyl) pyridine (3.2 g), Pd (PPh ₃ ) ₄ (320 mg), potassium triphosphate (4.8 g), 1,2,4-trimethylbenzene (10 ml), t-butyl Alcohol (2 mL) and water (0.5 mL) were placed in a flask and stirred for 4 hours at reflux under a nitrogen atmosphere, and after completion of heating, the reaction solution was cooled to room temperature, and water and toluene were added to carry out liquid separation. The solvent was distilled off under reduced pressure in the organic layer, the residue was purified by silica gel column chromatography (toluene / ethyl acetate = 80/20 (volume ratio)), and the compound '4,4'-(( 2-naphthalen-1-yl) anthracene-9,10-diyl) bis (3,1-phenylene) dipyridine "(2.2 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis example of the compound represented by Formula (1-2-1)>

[Formula 43]

<Synthesis of 2-([1,1'-biphenyl] -4-yl) anthracene>

2-bromoanthracene (100.0 g), [1,1'-biphenyl] -4-ylboronic acid (92.4 g), bis (dibenzylideneacetone) palladium (0) (1.1 g), tricyclohexylphosphine (1.1 g), tripotassium phosphate (310.0 g), 1,2,4-trimethylbenzene (1000 mL), t-butyl alcohol (200 mL) and water (40 mL) were placed in a flask, and refluxed under a nitrogen atmosphere. It stirred at the temperature for 3 hours and a half. After the completion of heating, the reaction solution was cooled at room temperature, stirred with addition of water, and then suction filtered to collect a solid. The obtained solid was washed with methanol, and then heptane, and 2-([1,1'-biphenyl] -4-yl) anthracene (128.0 g) was obtained.

<Synthesis of 2-([1,1'-biphenyl] -4-yl) -9,10-dibromoanthracene>

Bromine (100.0 g) was added dropwise to a flask containing 2-([1,1'-biphenyl] -4-yl) anthracene (93.6 g) and chloroform (2000 mL) at room temperature under a nitrogen atmosphere. After stirring overnight at room temperature, chlorobenzene (500 mL) was added and stirred at 80 ° C. for 4 hours. After completion | finish of reaction, the sodium hydrogencarbonate aqueous solution and then the sodium sulfite aqueous solution were added, and solid was collected by suction filtration. The obtained solid was washed with methanol, and then dissolved in heated chlorobenzene to remove insoluble content by decantation. The solution was cooled to room temperature, and the precipitated crystals were collected by suction filtration to obtain 2-([1,1'-biphenyl] -4-yl) -9,10-dibromoanthracene (126.0 g). Got it.

<2,2 '-(2-([1,1'-biphenyl] -4-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2 Synthesis of Dioxaborolane)

2-([1,1'-biphenyl] -4-yl) -9,10-dibromoanthracene (62.0 g), bispinacolatodiborone (77.5 g), bis (dibenzylideneacetone) palladium ( 0) A flask containing (7.30 g), tricyclohexylphosphine (8.55 g), potassium acetate (49.9 g), potassium carbonate (35.1 g) and anisole (760 mL) was heated under nitrogen atmosphere at 150 ° C. for 2.5 hours. It stirred by heating. After the completion of the heating, the reaction solution was cooled to room temperature, xylene (1000 mL) was added, and suction filtration was performed using a Kiriyama funnel covered with celite. After distilling off the filtrate under reduced pressure, heptane was added, and the obtained crystal was collected by suction filtration, and 2,2 '-(2-([1,1'-biphenyl] -4-yl) anthracene-9, 10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (51.8 g) was obtained.

<Synthesis example of the compound represented by Formula (1-2-1)>

2,2 '-(2-([1,1'-biphenyl] -4-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2- Dioxaborolane) (46.3 g), 4- (3-bromophenyl) pyridine (44.7 g), Pd (PPh ₃ ) ₄ (1.84 g), tripotassium phosphate (84.4 g), 1,2,4- Trimethylbenzene (260 mL), t-butyl alcohol (52 mL) and water (10 mL) were put into the flask, and the mixture was stirred at reflux for 2 hours under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature, water was added, suction filtration was performed, and a solid was collected. The obtained solid was washed with methanol and heated chlorobenzene. After recrystallization with orthodichlorobenzene, the product was purified by activated carbon column chromatography (chlorobenzene) to obtain the compound "4,4 '-((2-([1,1'-biphenyl) represented by formula (1-2-1). ] -4-yl) anthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine "(29.6 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis of Compound Represented by Formula (1-2-2)>

[Formula 44]

2,2 '-(2-([1,1'-biphenyl] -3-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2- Dioxaborolane) (67.6 g), 4- (3-bromophenyl) pyridine (65.2 g), Pd (PPh ₃ ) ₄ (6.7 g), tripotassium phosphate (98.5 g), 1,2,4- Trimethylbenzene (350 mL), t-butyl alcohol (70 mL) and water (14 mL) were put into the flask, and the mixture was stirred at reflux temperature under nitrogen atmosphere for 1 hour. After the completion of heating, the reaction solution was cooled to room temperature, and filtered by suction with a Kiriyama funnel covered with celite. The filtrate was distilled off under reduced pressure, and then methanol was added to precipitate a precipitate. The precipitate collected by suction filtration was washed with heated ethyl acetate and then purified by activated carbon column chromatography (toluene). Further purification was by silica gel column chromatography (toluene / ethyl acetate mixed solvent). At this time, referring to the method described in `` Introduction to Organic Chemistry Experiment (1) -Material Handling and Separation and Purification Method '', Chemical Drivers Publication, page 94, the ratio of ethyl acetate in the developing solution is gradually increased to elute the target product. I was. The solvent was distilled off under reduced pressure to obtain the compound "4,4 '-((2-([1,1'-biphenyl] -3-yl) anthracene-9,10-diyl represented by formula (1-2-2)] ) Bis (3,1-phenylene)) dipyridine "(21.3 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

<Synthesis of Compound Represented by Formula (1-2-4)>

[Formula 45]

2,2 '-(2- (naphthalen-2-yl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan) (68.1 g ), 4- (3-bromovenyl) pyridine (68.8 g), Pd (PPh ₃ ) ₄ (7.05 g), dipotassium phosphate (104 g), 1,2,4-trimethylbenzene (350 mL), t -Butanol (70 mL) and water (14 mL) were put into the flask, and the mixture was stirred for 1 hour at reflux under a nitrogen atmosphere. After the completion of heating, the reaction solution was cooled to room temperature and filtered by addition of water and heptane. The obtained solid was washed with water, methanol and then ethyl acetate. Furthermore, after wash | cleaning with heated chlorobenzene, it recrystallized with ortho-dichlorobenzene, and the compound "4,4 '-((2-naphthalen-2-yl) anthracene-9,10 represented by Formula (1-2-4). -Diyl) bis (3,1-phenylene) dipyridine "(36.2 g) was obtained.

The structure of the pyridylphenyl substituted anthracene compound obtained by NMR measurement was confirmed.

By changing the compound of a raw material suitably, the pyridylphenyl substituted anthracene compound other than this invention can be synthesize | combined by the method according to the synthesis example mentioned above.

Hereinafter, in order to demonstrate this invention further in detail, the Example of the organic electroluminescent element using the compound of this invention is shown, but this invention is not limited to these.

<Example about the compound represented by general formula (1-1)>

Example 1? The organic electroluminescent element which concerns on 5 and the comparative example 1 was produced, and the time (hr) to hold | maintain the drive start voltage (V) and 90% or more of brightness | luminance of an initial value in a constant current drive test was measured, respectively. Hereinafter, an Example and a comparative example are explained in full detail.

Example 1 produced? The material structure of each layer in the organic electroluminescent element which concerns on 5 and the comparative example 1 is shown in following Table 1. In addition, the negative electrode was composed of quinolinol lithium (Liq) / (magnesium + silver) in the whole.

Hole injection layer
(40 nm) Hole transport layer
(30 nm) Light emitting layer (35 nm) Electron transport layer
(15 nm) Host Dopant Example 1 HI NPD Compound (A) Compound (B) Compound (1-1-10) Example 2 HI NPD Compound (A) Compound (B) Compound (1-1-7) Example 3 HI NPD Compound (A) Compound (B) Compound (1-1-2) Example 4 HI NPD Compound (A) Compound (B) Compound (1-1-3) Example 5 HI NPD Compound (A) Compound (B) Compound (1-1-4) Comparative Example 1 HI NPD Compound (A) Compound (B) Compound (C)

In Table 1, "HI" is N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl] -4, 4'-diamine, "NPD" is N, N'- diphenyl-N, N'- dinaphthyl-4,4'- diaminobiphenyl, and compound (A) is 9-phenyl-10- (4- Phenylnaphthalen-1-yl) anthracene, compound (B) is N ⁵ , N ⁵ , N ⁹ , N ⁹ -7,7-hexaphenyl-7H-benz [C] fluorene-5,9-diamine, compound ( C) is 4,4 '-((2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine, and "Liq" is 8-quinolinolithium. The chemical structure is shown below.

[Formula 46]

&Lt; Example 1 >

<Device Using Compound (1-1-10) for Electron Transport Layer>

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offtoceance Co., Ltd.), which was polished to 150 nm by ITO formed into a film with a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Pore Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and a molybdenum containing compound (A) Molybdenum vapor deposition boat containing compound deposition boat, compound (B), Molybdenum vapor deposition boat containing compound (1-1-10) of the present invention, Molybdenum vapor deposition boat containing quinolinol lithium (Liq) , A molybdenum boat containing magnesium and a tungsten deposition boat containing silver were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum vessel was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited to a film thickness of 40 nm to form a hole injection layer, and then the deposition boat containing NPD was heated to The film was deposited to have a thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were simultaneously heated to be deposited so as to have a thickness of 35 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of compound (A) and compound (B) was approximately 95 to 5. Next, the vapor deposition boat containing the compound (1-1-10) was heated to be vapor deposited so as to have a film thickness of 15 nm to form an electron transporting layer. The deposition rate of each layer is 0.01? 1 nm / second.

Thereafter, the vapor deposition boat containing quinolinolithium (Liq) was heated to have a thickness of 0.O1? Deposited at a deposition rate of 0.1 nm / second. Subsequently, the boat containing magnesium and the boat containing silver were simultaneously heated to be deposited so as to have a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10 to 1, and the cathode was formed so that the deposition rate was from 0.1 nm to 10 nm / second to obtain an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. Moreover, the constant current drive test was done by the current density for obtaining an initial luminance of 2000 cd / m <2>. As a result, the drive test starting voltage was 4.89 V, and time to hold | maintain brightness | luminance of 90% (1800 cd / m <2>) or more of initial value was 206 hours.

<Example 2>

<Element which used compound (1-1-7) for the electron carrying layer>

An organic EL device was obtained by the method according to Example 1 except that compound (1-1-10) was changed to compound (1-1-7). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was conducted by the current density for obtaining an initial luminance of 2000 cd / m 2. As a result, the drive test start voltage was 5.31 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 158 hours.

<Example 3>

<Element which used compound (1-1-2) for the electron carrying layer>

An organic EL device was obtained by the method according to Example 1 except that compound (1-1-10) was changed to compound (1-1-2). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was conducted by the current density for obtaining an initial luminance of 2000 cd / m 2. As a result, the drive test start voltage was 5.24 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 104 hours.

<Example 4>

<Element which used compound (1-1-3) for the electron carrying layer>

An organic EL device was obtained by the method according to Example 1 except that compound (1-1-10) was changed to compound (1-1-3). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was conducted by the current density for obtaining an initial luminance of 2000 cd / m 2. As a result, the drive test start voltage was 5.26 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 103 hours.

Example 5

<Element which used compound (1-1-4) for the electron carrying layer>

An organic EL device was obtained by the method according to Example 1 except that compound (l-1-10) was changed to compound (1-1-4). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was conducted by the current density for obtaining an initial luminance of 2000 cd / m 2. As a result, the drive test start voltage was 5.48 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 148 hours.

Comparative Example 1

An organic EL device was obtained by the method according to Example 1 except that compound (1-10) was changed to compound (C). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was conducted by the current density for obtaining an initial luminance of 2000 cd / m 2. As a result, the drive test start voltage was 5.13 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 66 hours.

The above result was put together in Table 2.

Material of electron transport layer  Drive start voltage (V) at 2000 cd / m2 light emission The time (hours) that the luminance keeps more than 90% of the initial luminance Example 1 Compound (1-1-10) 4,89 206 Example 2 Compound (1-1-7) 5.31 158 Example 3 Compound (1-1-2) 5.24 104 Example 4 Compound (1-1-3) 5.26 103 Example 5 Compound (1-1-4) 5.48 148 Comparative Example 1 Compound (C) 5.13 66

<Example about the compound represented by General formula (1-2)>

The organic electroluminescent element which concerns on Example 6, 7 and the comparative example 2 was produced, and the drive start voltage (V) in the constant current drive test, and the time (hr) which hold | maintain 90% or more of brightness | luminance of an initial value were respectively measured. . Hereinafter, an Example and a comparative example are explained in full detail.

The material structure of each layer in the produced organic EL element which concerns on Example 6, 7 and Comparative Example 2 is shown in following Table 3. In addition, the negative electrode was composed of quinolinol lithium (Liq) / (magnesium + silver) in the whole.

Hole injection layer
(40 nm) Hole transport layer
(30 nm) Light emitting layer (35 nm) Electron transport layer
(15 nm) Host Dopant Example 6 HI NPD Compound (A) Compound (B) Compound (1-2-10) Example 7 HI NPD Compound (A) Compound (B) Compound (1-2-2) Comparative Example 2 HI NPD Compound (A) Compound (B) Compound (D)

In Table 3, "HI" is N ^4, N ^{4 '-} diphenyl -N ^4, N ^4' - bis (9-phenyl -9H- carbazole-3-yl) [1,1'-biphenyl] -4,4'-diamine, "NPD" is N ⁴ , N ^{4 '} -di (naphthalen-1-yl) -N ⁴ , N ^4' -diphenyl- [1,1'-biphenyl] -4, 4'-diamine, Compound (A) is 9-phenyl-10- (4-phenylnaphthalen`-1-yl) anthracene, Compound (B) is N ⁵ , N ⁵ , N ⁹ , N ⁹ -7,7- Hexaphenyl-7H-benzo [C] fluorene-5,9-diamine, compound (D) is 4,4 '-((2-phenylanthracene-9,10-diyl) bis (3,1-phenylene) Dipyridine and Liq are 8-quinolinolithium. The chemical structure is shown below.

[Formula 47]

<Example 6>

<Device Using Compound (1-2-10) for Electron Transport Layer>

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offtoceance Co., Ltd.), which was polished to 150 nm by ITO formed into a film with a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Vacuum Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and a molybdenum compound (A) were added. Evaporation boat, molybdenum evaporation boat containing compound (B), molybdenum evaporation boat containing compound (1-2-10) of the present invention, molybdenum evaporation boat containing quinolinol lithium (Liq), A molybdenum boat containing magnesium and a tungsten deposition boat containing silver were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum vessel was decompressed to 5 × 10 ⁻⁴ Pa, and the deposition boat containing HI was first heated to be deposited to a film thickness of 40 nm to form a hole injection layer. Then, the deposition boat containing NPD was heated to form a film. It was deposited so as to have a thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were simultaneously heated to be deposited so as to have a thickness of 35 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of compound (A) and compound (B) was approximately 95 to 5. Next, the steaming boat containing the compound (1-2-10) was heated to be deposited so as to have a film thickness of 15 nm to form an electron transporting layer. The deposition rate of each layer is 0.01? 1 nm / second.

Thereafter, the vapor deposition boat containing quinolinolithium (Liq) was heated to have a thickness of 0.O1? Deposited at a deposition rate of 0.1 nm / second. Subsequently, the boat containing magnesium and the boat containing silver were simultaneously heated to be deposited so as to have a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10 to 1, and the deposition rate was 0.1? The cathode was formed so as to be 10 nm / second to obtain an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. Moreover, the constant current drive test was done by the current density for obtaining an initial luminance of 2000 cd / m <2>. As a result, the drive test start voltage was 5.31 V, and time to hold | maintain the brightness | luminance of 90% (1800 cd / m <2>) or more of initial value was 140 hours.

<Example 7>

<Device Using Compound (1-2-2) in Electron Transport Layer>

An organic EL device was obtained by the method according to Example 6 except that compound (1-2-10) was changed to compound (1-2-2). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was conducted by the current density for obtaining an initial luminance of 2000 cd / m 2. As a result, the drive test start voltage was 5.65 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 216 hours.

Comparative Example 2

An organic EL device was obtained by the method according to Example 6 except that compound (1-2-10) was changed to compound (D). The ITO electrode is used as the anode, and the magnesium / silver electrode is used as the cathode. The constant current drive test was performed by the current density for obtaining initial stage luminance of 200 cd / m <2>. As a result, the drive test start voltage was 5.15 V, and time to hold | maintain 90% or more of brightness | luminance of an initial value was 68 hours.

The above result was put together in Table 4.

Material of electron transport layer  Drive start voltage (V) at 2000 cd / m2 light emission The time (hours) that the luminance keeps more than 90% of the initial luminance Example 6 Compound (1-2-10) 5.31 140 Example 7 Compound (1-2-2) 5.65 216 Comparative Example 2 Compound (C) 5.15 68

According to a preferred embodiment of the present invention, it is possible to provide an organic electroluminescent element, a display device having the same, a lighting device having the same, and the like, in particular, which improves the lifespan of the light emitting device and is excellent in balance with the driving voltage.

100 organic electroluminescent devices
101 boards
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 (10)

The electron transport material containing the compound represented by following General formula (1).
[Formula 1]

(1) In formula (1), Ar is carbon number 10? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, the 4-pyridyl group may be connected together to the 3 or 4 position of phenyl, and at least 1 hydrogen in the compound represented by Formula (1) may be substituted by deuterium. The electron transport material containing the compound represented by following General formula (1-1).
(2)

In formula (1-1), Ar is C10? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, and at least 1 hydrogen in the compound represented by Formula (1-1) may be substituted by deuterium. The electron transport material containing the compound represented by following General formula (1-2).
(3)

In formula (1-2), Ar is carbon number 10? It is aryl of 24, and the said aryl has C1-C? 12 alkyl, 3? 12 cycloalkyl or 6? It may be substituted by 20 aryl, and at least 1 hydrogen in the compound represented by Formula (1-2) may be substituted by deuterium. The method according to any one of claims 1 to 3,
Ar is biphenylyl, terphenylyl or naphthyl, and the said naphthyl may be substituted by phenyl. The method according to any one of claims 1 to 3,
Ar is 3-biphenylyl, 4-biphenylyl, m-terphenyl-5'-yl, 1-naphthyl or 2-naphthyl. A pair of electrodes consisting of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and an electron transporting material according to any one of claims 1 to 5, which is disposed between the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer. The method according to claim 6,
At least one of the electron transporting layer and the electron injecting layer further contains an organic containing at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, a borane derivative and a benzimidazole derivative. EL device. The method according to claim 6 or 7,
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 oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, an halide of an alkaline earth metal, and an oxide of a rare earth metal. And an organic electroluminescent device comprising at least one selected from the group consisting of halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals. The display device provided with the organic electroluminescent element in any one of Claims 6-8. The illuminating device provided with the organic electroluminescent element in any one of Claims 6-8.

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